Process for functionalization of unsaturated compounds

ABSTRACT

The present invention relates to a process for synthesizing a multifunctional compound, including the reaction of a compound of formula (II) with atmospheric or molecular oxygen, in the presence of at least one aldehyde of formula (III), and optionally in the presence of at least one catalyst or at least one radical initiator; wherein: R 10 , R 20 , R 30 , R 40 , R 50 , L 2 , R 60 , R 7 , R 8 , and R 9  are as described in the claims. The invention also relates to the use of these compounds as monomers for the preparation of polyurethane. The invention also relates to the use of these compounds as monomers of polymers or of biopolymers.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the U.S. National Phase under 35 U.S.C. §371 ofInternational Application PCT/EP2011/068824, filed Oct. 27, 2011, whichwas published in a non-English language, which claims priority to EP10290581.7, filed Oct. 27, 2010.

FIELD OF THE INVENTION

The invention relates to a method for synthesizing functionalizedcompounds, starting from unsaturated molecules. The invention alsorelates to the use of these compounds as surfactants, plasticizers,lubricants, monomers of polymers or monomers of biopolymers, etc.

DESCRIPTION OF THE PRIOR ART

The synthesis of compounds from unsaturated molecules may be carried outin several ways. For example, it may be carried out in two steps throughan epoxidation route. The first step includes an epoxidation reaction byoxygenated water in the presence of a carboxylic acid in order to form aperacid in situ that comprises the epoxidation agent. On an industrialscale, acetic acid is used in the presence of a mineral acid (H₂SO₄)that is necessary in order to catalyze the formation of the peracid. Thesecond step includes the reaction opening of the oxirane cycle using acleaving agent in the presence of a homogenous acid-base catalyticsystem.

The homogenous catalysts frequently used in the case of an opening offatty epoxides are hydrochloric acid, sulfuric acid, phosphoric acid,fluoroboric acid or p-toluenesulfonic acid. Regarding the first step,the peracid is the primary cause of secondary reactions of opening theoxirane cycle during the industrial process, which causes a selectivityof fatty epoxides which rarely exceeds 80%. In addition, the mineralacid in an oxidizing environment causes serious corrosion issues, whichmay have consequences on use, storage and transport. Regarding thesecond step, the homogenous catalysts used must be neutralized, whichnecessitates additional steps that very often produce waste. Thesetechnologies involve many secondary reactions that unquestionably have anegative impact on the selectivity of the reaction.

The purpose of the present invention is to remedy at least one of thedifficulties cited above.

SUMMARY OF THE INVENTION

The present invention relates to a process for synthesizing compounds offormula (Ia) or (Ib), a stereoisomer, a mixture thereof, an oligomerand/or a polymer thereof:

comprising the reaction of a compound having formula (II) withatmospheric or molecular oxygen, in the presence of at least onealdehyde of formula (III) and optionally in the presence of at least onecatalyst or at least one radical initiator;

wherein:

R¹ is H or is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆-C₁₂ aryl, with each group being optionally substitutedby one or several groups, either identical or different, selected fromthe group comprising a halogen atom, —OH, —CHO, oxo, cyano, —NR⁹ ₂,epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOL¹R⁵, —OCOR⁸, and—CO₂R⁶⁰;

R² is H, cyano or a halogen atom, or is selected from the groupcomprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂arylC₁₋₆ alkyl, with each group being optionally substituted by one orseveral groups, either identical or different, selected from the groupcomprising a halogen atom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOL¹R⁵, —OCOR⁸, and —CO₂R⁶⁰;

R³ is selected from the group comprising epoxy, —OCOR⁸, —CO₂R⁸, C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂arylC₁₋₆ alkyl, with eachgroup being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl,C₆-C₁₂ aryl, —OCOL¹R⁵, —OCOR⁸, and —CO₂R⁶⁰;

R⁴ is H, cyano, a halogen atom, or is selected from the group comprisingC₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with each group beingoptionally substituted by one or several groups, either identical ordifferent, selected from the group comprising a halogen atom, —OH, —CHO,oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl,—OCOL¹R⁵, —OCOR⁸, and —CO₂R⁶⁰;

or R¹ and R³ may, with the carbons to which they are bound, form a groupselected from a C₅-C₁₂ cycloalkyl and a C₅-C₁₂ cycloalkenyl, with eachgroup being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, oxo, cyano, epoxy, —OCOL¹R⁵, —OCOR⁸, —CO₂R⁶⁰, C₁-C₆ alkyl,C₁-C₆ hydroxyalkyl, and C₂-C₆ alkenyl;

R⁵ is selected from the group comprising H, a halogen atom, —OH, —CHO,epoxy, —SR⁸, cyano, nitro, isocyanate, C₁-C₂₀ alkyl, C₁-C₄ alkoxy,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, heterocycloalkyl, —CO₂R⁸, and —NR⁹ ₂;

R⁶ is H or —CO-L¹-R⁵;

L¹ is a single covalent bond, or is selected from the group comprisingC₁-C₂₀ alkylene, C₃-C₁₂ cycloalkylene, C₂-C₁₂ alkenylene,C₅-C₁₂cycloalkenylene, C₆-C₁₂ arylene, heteroarylene, andheterocycloalkylene, with each group being optionally substituted by oneor several groups, either identical or different either identical ordifferent, selected from the group comprising a halogen atom, —OH, oxo,nitro, —CHO, —OCOL¹R⁵, —CO₂R⁶⁰, —NR⁹ ₂, C₁-C₆ alkyl, C₁-C₄ alkoxy,C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, C₆-C₁₂arylC₁₋₆ alkyl, C₁-C₆ hydroxyalkyl,and C₁₋₆ alkylC₆-C₁₂ aryl;

R¹⁰ is H, or is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆-C₁₂ aryl, with each group being optionally substitutedby one or several groups, either identical or different either identicalor different, selected from the group comprising a halogen atom, —OH,—CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl,C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰;

R²⁰ is H, cyano, a halogen atom, or —CHO, or is selected from the groupcomprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂arylC₁₋₆ alkyl, with each group being optionally substituted by one orseveral groups, either identical or different, selected from the groupcomprising a halogen atom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰,

R³⁰ is selected from the group comprising epoxy, —OCOR⁸, —CO₂R⁸, C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂ arylC₁₋₆alkyl, with eachgroup being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰,C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰,

R⁴⁰ is H, cyano, a halogen atom, or —CHO, or is selected from the groupcomprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with eachgroup being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰,C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰;

or R¹⁰ and R³⁰ may, with the carbons to which they are bound, form agroup selected from a C₅-C₁₂ cycloalkyl or a C₅-C₁₂ cycloalkenyl, witheach group being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, —CHO, cyano, oxo, epoxy, —OCOR⁸, —CO₂R⁶⁰, —OCOL²R⁵⁰, C₁-C₆alkyl, C₁-C₆ hydroxyalkyl, and C₂-C₆ alkenyl;

R⁵⁰ is selected from the group comprising H, —CHO, epoxy, a halogenatom, —OH, cyano, nitro, isocyanate, C₁-C₂₀ alkyl, C₁-C₄ alkoxy, C₂-C₂₀alkenyl, C₂-C₂₀ alkynyl, heterocycloalkyl, —CO₂R⁸, and —NR⁹ ₂;

L² is a single covalent bond, or is selected from the group comprisingC₁-C₂₀ alkylene, C₃-C₁₂ cycloalkylene, C₂-C₁₂ alkenylene, C₅-C₁₂cycloalkenylene, C₆-C₁₂ arylene, heteroarylene, and heterocycloalkylene,with each group being optionally substituted by one or several groups,either identical or different, selected from the group comprising ahalogen atom, oxo, nitro, —CHO, —OH, —NR⁹ ₂, C₁-C₆ alkyl, C₁-C₄ alkoxy,C₆-C₁₂ arylC₁₋₆ alkyl, C₁₋₆ alkylC₆-C₁₂ aryl, C₆-C₁₂ aryloxy, C₁-C₆hydroxyalkyl, and C₆-C₁₂ aryl;

R⁶⁰ is selected from the groups comprising H or C₁-C₆ alkyl optionallysubstituted by one or several groups, either identical or different,selected from the group comprising —OH, —CHO, —O—COR⁷, and C₁-C₆ alkyl;

R⁷ is selected from the group comprising C₁-C₂₄ alkyl, C₂-C₂₀ alkenyl,and C₆-C₁₂ aryl, with each group being optionally substituted by one orseveral groups, either identical or different, selected from the groupcomprising —OH, epoxy and —OCOL¹R⁵;

R⁸ is selected from among H or C₁-C₆ alkyl; and R⁹ is selected from H,C₁-C₆ alkyl, or C₆-C₁₂ aryl.

The process according to the present invention draws its innovation, inrelation to current processes, from the reduction of the steps ofsynthesis as well as from the envisaged synthesis method. The chemicalreactions involved in the process according to the invention use oxygenas the transformation agent, which avoids on the one hand the risksrelated to the storage and transport of oxygenated water (traditionallyused for the fabrication of epoxides) and on the other hand considerablyreduces production cost, since oxygen may be taken from ambient air(atmospheric oxygen). According to a preferred embodiment, to beconducted under these conditions, the synthesis requires the presence ofa mineral solid (catalyst). According to a preferred embodiment, thecatalyst plays an essential role since on the one hand it acceleratesthe chemical reactions, it decreases their energy demand, and on theother hand it considerably simplifies the fabrication process. Thisprocess allows “cleaner” synthesis thus reducing fabrication costs. Themultifunctional compounds produced by the reaction, also called“monomers,” may also react with each other during the reaction toproduce “dimers” which in turn may react with the various monomers toproduce very varied oligomers (trimers, quadrimers, etc.), and polymers.

The invention therefore proposes an original, economical and ecologicalprocess for the production of multifunctional compounds, the latter maybe the basis for the production of very diverse products, and inparticular plastic material or lubricants, etc. The synthesizedmolecules are particularly beneficial as synthons for the fabrication ofplastic material. Advantageously, the synthesized molecules maythemselves even be oligomers or polymers. Various types of polymers maybe envisaged depending on the nature of the function provided by thesynthesis process. When the unsaturated and/or aldehydic compound usedin the process is derived from the plant world (fatty acid esters), theplastic materials or polymers manufactured downstream from the synthesisprocess will therefore be produced from the start from a renewable rawmaterial, and therefore they are qualified as biopolymers or even“bio-based polymers.”

The present invention also relates to a compound of formula (Ie) or(If), a stereoisomer thereof, or a mixture thereof;

wherein:

R¹⁶ is H or is selected from the group comprising —CO—(CR²¹R²²)_(q)—R²³,—CO—C₆-C₁₂aryl and —CO—C₅-C₁₂cycloalkenyl, with each group beingoptionally substituted by one or several groups, either identical ordifferent, selected from the group comprising a halogen atom, —OH,—OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;

R¹⁷ is selected from the group comprising a C₂-C₂₀ alkyl and a C₂-C₂₀alkenyl,

with each group being optionally substituted by one or several groups,either identical or different, selected from the group comprising aC₁-C₆ alkyl, a C₆ aryl, —OR¹⁶ and —CO₂R²⁴;

R¹⁸ is H or is selected from the group comprising a C₂-C₂₀ alkyl and aC₂-C₂₀ alkenyl, with each group being optionally substituted by one orseveral groups, either identical or different, selected from the groupcomprising a C₁-C₆ alkyl, a C₆ aryl, —OR¹⁶ and CO₂R²⁴;

or R¹⁷ and R¹⁸ may, with the carbons to which they are bound, form agroup selected from a C₅-C₁₂ cycloalkyl or a C₅-C₁₂ cycloalkenyl, witheach group being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OR¹⁶, —OCOR¹⁹, —CO₂R²⁴, and a C₁-C₆ alkyl;

R¹⁹ is selected from the group comprising —(CR²¹R²²)_(q)—R²³, a C₆-C₁₂aryl, and a C₅-C₁₂ cycloalkenyl, with each group being optionallysubstituted by one or several groups, either identical or different,selected from the group comprising a halogen atom, —OH, —OCOR¹⁹,—CO₂R²⁴, and C₁-C₆ alkyl;

q is a whole number comprised between 3 and 12;

each identical or different R²¹ is selected from H or a C₁-C₆ alkyl;

each identical or different R²² is selected from H or a C₁-C₆ alkyl;

R²³ is H or —OH, or is selected from the group comprising C₁-C₆ alkyland a C₆-C₁₂ aryl, with each group being optionally substituted by oneor several groups, either identical or different, selected from thegroup comprising a halogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;

R²⁴ is H or a C₁-C₆ alkyl optionally substituted by one or severalgroups, either identical or different, selected from the groupcomprising —OH, —O—COR²⁵, and C₁-C₆ alkyl; and

R²⁵ is selected from the group comprising C₂-C₂₀ alkyl, and C₂-C₂₀alkenyl, with each group being optionally substituted by one or severalgroups, either identical or different, selected from the groupcomprising —OH, epoxy, —OR¹⁶, and —OCOR¹⁹.

According to a preferred embodiment, the present invention also relatesto a compound having formula (Ie) or (If), a stereoisomer thereof, or amixture thereof; provided that the compound is not methyl9-(hexanoyloxy)-10-hydroxyoctadecanoate, methyl10-(hexanoyloxy)-9-hydroxyoctadecanoate, the octanoic ester of methylhydroxyoleate, the 2-ethyl-hexyl ester of methyl hydroxyoleate, methylhydroxybenzoyloxy-octadodecanoate, 1,2-heptanediol dicaproate or1,2-octanediol dicaproate.

The present invention also concerns the use of compounds according tothe invention, in the preparation of polymers, of biopolymers, ofsurfactants, plasticizers, lubricants and biocides. Preferably, theinvention concerns the use of the compounds according to the invention,in the preparation of polymers or biopolymers. This invention alsoconcerns the use of a compound according to the invention, as a monomerfor the preparation of polyurethane.

Other aspects, distinctive aspects and advantages of the presentinvention will be gleaned from reading the description that follows andthe illustrative examples provided simply by way of illustration, andwhich are not intended in any way to limit the scope of the invention.

BRIEF DESCRIPTION OF FIGURES

FIG. 1 presents a graph showing the kinetic reagent conversion curvesand yield of products in the case of the reaction of hexanal with4-octene in Example 3.

FIG. 2 presents a graph showing the evolution of the composition of thereaction medium as a function of time for the reaction of Example 4.

FIG. 3 presents the infrared spectra of the functionalized product fromExample 5, in the presence of di-isocyanate before polymerization (t=0min) and after polymerization (t=240 min).

FIG. 4 presents the infrared spectra of the product functionalized fromExample 6 before polymerization (t=0 min) and after polymerization (t=30min).

FIG. 5 presents a graph showing selectivity of functionalized productsas a function of the yield for the catalysts tested in Example 7.

DETAILED DESCRIPTION OF THE INVENTION

According to a first aspect, the present invention concerns a processfor synthesizing multifunctional compounds: comprising the reaction of acompound of formula (II) with atmospheric or molecular oxygen, in thepresence of at least one aldehyde of formula (III), and optionally inthe presence of at least one catalyst or at least one radical initiator;

wherein:

R¹⁰ is H, or is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆-C₁₂ aryl, with each group being optionally substitutedby one or several groups, either identical or different, selected fromthe group comprising a halogen atom, —OH, —CHO, oxo, cyano, —NR⁹ ₂,epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and—CO₂R⁶⁰;

R²⁰ is H, cyano, a halogen atom, or —CHO, or is selected from the groupcomprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂arylC₁₋₆alkyl, with each group being optionally substituted by one orseveral groups, either identical or different, selected from the groupcomprising a halogen atom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰;

R³⁰ is selected from the group comprising epoxy, —OCOR⁸, —CO₂R⁸, C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂arylC₁₋₆ alkyl, with eachgroup being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰,C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰;

R⁴⁰ is H, cyano, a halogen atom, or —CHO, or is selected from the groupcomprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with eachgroup being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰,C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰;

or R¹⁰ and R³⁰ may, with the carbons to which they are bound, form agroup selected from a C₅-C₁₂ cycloalkyl or a C₅-C₁₂ cycloalkenyl, witheach group being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, —CHO, cyano, oxo, epoxy, —OCOR⁸, —CO₂R⁶⁰, —OCOL²R⁵⁰, C₁-C₆alkyl, C₁-C₆ hydroxyalkyl, and C₂-C₆ alkenyl

R⁵⁰ is selected from the group comprising H, —CHO, epoxy, a halogenatom, —OH, —SR⁸, cyano, nitro, isocyanate, C₁-C₂₀ alkyl, C₁-C₄ alkoxy,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, heterocycloalkyl, —CO₂R⁸, and —NR⁹ ₂;

L² is a single covalent bond, or is selected from the group comprisingC₁-C₂₀ alkylene, C₃-C₁₂ cycloalkylene, C₂-C₁₂ alkenylene, C₅-C₁₂cycloalkenylene, C₆-C₁₂ arylene, heteroarylene, and heterocycloalkylene,with each group being optionally substituted by one or several groups,either identical or different, selected from the group comprising ahalogen atom, oxo, nitro, —CHO, —OH, —NR⁹ ₂, C₁-C₆ alkyl, C₁-C₄ alkoxy,C₆-C₁₂ arylC₁₋₆alkyl, C₆-C₁₂ aryloxy, C₁₋₆ alkylC₆-C₁₂ aryl, C₁-C₆hydroxyalkyl, and C₆-C₁₂ aryl;

R⁶⁰ is selected from the group comprising H and C₁-C₆ alkyl optionallysubstituted by one or several groups, either identical or different,selected from the group comprising —OH, —CHO, —O—COR⁷, and C₁-C₆ alkyl;

R⁷ is selected from the group comprising C₁-C₂₄ alkyl, C₂-C₂₀ alkenyl,and C₆-C₁₂ aryl, with each group being optionally substituted by one orseveral groups, either identical or different, selected from the groupcomprising —OH, epoxy and —OCOL¹R⁵;

R⁸ is selected from H or C₁-C₆ alkyl; and

each identical or different R⁹ is selected from H, C₁-C₆ alkyl, orC₆-C₁₂ aryl.

Preferably, the present invention concerns a process for synthesisaccording to the first aspect in which the multifunctional compound orcompounds are a compound of formula (Ia) of (Ib), a stereoisomer, amixture of compounds of this family, and/or an oligomer and/or a polymerthereof.

The present invention preferably concerns a process for the synthesis ofcompounds of the family represented by formula (Ia) or (Ib), astereoisomer, a mixture of compounds of this family, and/or an oligomerand/or a polymer thereof, such as the compounds of formula (Ic) or (Id),

comprising the reaction of an unsaturated molecule of formula (II) withatmospheric or molecular oxygen, in the presence of at least onealdehyde of formula (III) and optionally in the presence of at least onecatalyst or at least one radical initiator; wherein:

p is a whole number comprised between 1 and 10,000, preferably p is awhole number comprised between 1 and 1,000, for example p is a wholenumber comprised between 1 and 100;

R¹ is H or is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆-C₁₂ aryl, each group being optionally substituted by oneor several groups (for example 1, 2, 3, or 4), either identical ordifferent, selected from the group comprising a halogen atom, —OH, —CHO,oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl,—OCOL¹R⁵, —OCOR⁸, and —CO₂R⁶⁰; preferably R¹ is H or is selected fromthe group comprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, witheach group being optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from the group comprising —OH, —CHO,oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl,—OCOL¹R⁵, —OCOR⁸, and —CO₂R⁶⁰; preferably R¹ is H or is selected fromthe group comprising C₁-C₂₀ alkyl, and C₂-C₂₀ alkenyl, with each groupbeing optionally substituted by 1, 2 or 3 groups, either identical ordifferent, selected from the group comprising —OH, oxo, C₁-C₂ alkoxy,C₁-C₆ alkyl, —OCOL¹R⁵, and —CO₂R⁶⁰; preferably R¹ is H or is selectedfrom the group comprising C₁-C₁₂ alkyl, and C₂-C₁₂ alkenyl, with eachgroup being optionally substituted by 1, 2 or 3 groups, either identicalor different, selected from the group comprising —OH, C₁-C₆ alkyl,—OCOL¹R⁵, and —CO₂R⁶⁰;

R² is H, cyano, or a halogen atom, or is selected from the groupcomprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂arylC₁₋₆alkyl, each group being optionally substituted by one or severalgroups (for example 1, 2, 3, or 4), either identical or different,selected from the group comprising a halogen atom, —OH, —CHO, oxo,cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOL¹R⁵,—OCOR⁸, and —CO₂R⁶⁰; preferably R² is H or is selected from the groupcomprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂arylC₁₋₆ alkyl, with each group being optionally substituted by 1, 2 or3 groups, either identical or different, selected from the groupcomprising —OH, —CHO, epoxy, oxo, cyano, —NR⁹ ₂, C₁-C₄ alkoxy, C₁-C₆alkyl, C₆-C₁₂ aryl, —OCOL¹R⁵, —OCOR⁸, and —CO₂R⁶⁰; preferably R² is H oris selected from the group comprising C₁-C₂₀ alkyl, and C₂-C₂₀ alkenyl,with each group being optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from the group comprising oxo, C₁-C₂alkoxy, C₁-C₆ alkyl, —OCOL¹R⁵, and —CO₂R⁶⁰; preferably R² is H or isselected from the group comprising C₁-C₁₂ alkyl, and C₂-C₁₂ alkenyl,with each group being optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from C₁-C₆ alkyl, —OCOL¹R⁵, or —CO₂R⁶⁰;preferably R² is H or a C₁-C₁₂ alkyl, optionally substituted by 1, 2 or3 groups, either identical or different, selected from C₁-C₆ alkyl,—OCOL¹R⁵, or —CO₂R⁶⁰, preferably R² is H;

R³ is selected from the group comprising epoxy, —OCOR⁸, —CO₂R⁸, C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂ arylC₁₋₆ alkyl, eachgroup being optionally substituted by one or several groups (for example1, 2, 3, or 4), either identical or different, selected from the groupcomprising a halogen atom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOL¹R⁵, —OCOR⁸, and —CO₂R⁶⁰;preferably R³ is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆-C₁₂ aryl, with each group being optionally substitutedby 1, 2 or 3 groups, either identical or different, selected from thegroup comprising —OH, —CHO, oxo, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl,C₆-C₁₂ aryl, —OCOL¹R⁵ and —CO₂R⁶⁰; preferably R³ is selected from thegroup comprising C₁-C₂₀ alkyl, and C₂-C₂₀ alkenyl, with each group beingoptionally substituted by 1, 2 or 3 groups, either identical ordifferent, selected from the group comprising —OH, oxo, C₁-C₂ alkoxy,C₁-C₆ alkyl, —OCOL¹R⁵ and —CO₂R⁶⁰; preferably R³ is selected from thegroup comprising C₁-C₁₂ alkyl, and C₂-C₁₂ alkenyl, with each group beingoptionally substituted by 1, 2 or 3 groups, either identical ordifferent, selected from —OH, C₁-C₆ alkyl, —OCOL¹R⁵, or —CO₂R⁶⁰;

R⁴ is H, cyano, or a halogen atom, or is selected from the groupcomprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, each groupbeing optionally substituted by one or several groups (for example 1, 2,3, or 4), either identical or different, selected from the groupcomprising a halogen atom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOL¹R⁵, —OCOR⁸, and —CO₂R⁶⁰;preferably R⁴ is H, or is selected from the group comprising C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with each group being optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising —OH, —CHO, oxo, epoxy, C₁-C₄ alkoxy, C₁-C₆alkyl, C₆-C₁₂ aryl, —OCOL¹R⁵, and —CO₂R⁶⁰; preferably R⁴ is H, or isselected from the group comprising C₁-C₂₀ alkyl, and C₂-C₂₀ alkenyl,with each group being optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from the group comprising oxo, C₁-C₂alkoxy, C₁-C₆ alkyl, —OCOL¹R⁵, and —CO₂R⁶⁰; preferably R⁴ is H, or isselected from the group comprising C₁-C₁₂ alkyl, and C₂-C₁₂ alkenyl,with each group being optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from C₁-C₆ alkyl, —OCOL¹R⁵, or —CO₂R⁶⁰;preferably R⁴ is H or C₁-C₁₂ alkyl, optionally substituted by 1, 2 or 3groups, either identical or different, selected from C₁-C₆ alkyl,—OCOL¹R⁵, or —CO₂R⁶⁰; preferably R⁴ is H; or else R¹ and R³ may, withthe carbons to which they are bound, form a group selected from a C₅-C₁₂cycloalkyl or a C₅-C₁₂ cycloalkenyl, each group being optionallysubstituted by one or several groups (for example 1, 2, 3, or 4), eitheridentical or different, selected from the group comprising a halogenatom, —OH, oxo, cyano, epoxy, —OCOL¹R⁵, —OCOR⁸, —CO₂R⁶⁰, C₁-C₆ alkyl,C₁-C₆ hydroxyalkyl, and C₂-C₆ alkenyl; or else R¹ and R³ may preferably,with the carbons to which they are bound, form a group selected from aC₅-C₁₂ cycloalkyl or a C₅-C₁₂ cycloalkenyl, with each group beingoptionally substituted by 1, 2, 3 or 4 groups, either identical ordifferent, selected from the group comprising an —OH, oxo, epoxy,—OCOL¹R⁵, —OCOR⁸, —CO₂R⁶⁰, C₁-C₆ alkyl, and C₂-C₆ alkenyl; or else R¹and R³ may preferably, with the carbons to which they are bound, form agroup selected from a C₅-C₁₀ cycloalkyl or a C₅-C₁₀ cycloalkenyl, witheach group being optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from —OH, epoxy, C₁-C₆ alkyl, or C₂-C₆alkenyl;

R⁵ is selected from the group comprising H, a halogen atom, —OH, —CHO,epoxy, —SR⁸, cyano, nitro, isocyanate, C₁-C₂₀ alkyl, C₁-C₄ alkoxy,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, heterocycloalkyl, —CO₂R⁸, and —NR⁹ ₂;preferably R⁵ is selected from the group comprising Cl, F, I, Br, —OH,—SH, —CHO, epoxy, cyano, nitro, isocyanate, C₁-C₄ alkoxy, C₂-C₁₂alkenyl, C₂-C₁₂ alkynyl, heterocycloalkyl, —CO₂R⁸, and —NR⁹ ₂;preferably, R⁵ is selected from the group comprising Cl, F, I, Br, —OH,—CHO, epoxy, —SH, cyano, and nitro; preferably —OH, —SH, epoxy, cyano ornitro; preferably —OH, —SH, epoxy or cyano;

R⁶ is H or —CO-L¹-R⁵;

L¹ is a single covalent bond, or is selected from the group comprisingC₁-C₂₀ alkylene, C₃-C₁₂ cycloalkylene, C₂-C₁₂ alkenylene, C₅-C₁₂cycloalkenylene, C₆-C₁₂ arylene, heteroarylene, and heterocycloalkylene,each group being optionally substituted by one or several groups (forexample 1, 2, 3, or 4), either identical or different, selected from thegroup comprising a halogen atom, —OH, oxo, nitro, —CHO, —OCOL¹R⁵,—CO₂R⁶⁰, —NR⁹ ₂, C₁-C₆ alkyl, C₁-C₄ alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy,C₆-C₁₂ arylC₁₋₆ alkyl, C₁-C₆ hydroxyalkyl, and C₁₋₆ alkylC₆-C₁₂aryl;preferably L¹ is a single covalent bond, or is selected from the groupcomprising C₁-C₂₀ alkylene, C₃-C₁₂ cycloalkylene, C₅-C₁₂ cycloalkenyleneand C₆-C₁₂ arylene, with each group being optionally substituted by 1,2, 3 or 4 groups, either identical or different, selected from the groupcomprising a halogen atom, —OH, oxo, —CHO, —OCOL¹R⁵, —CO₂R⁶⁰, —NR⁹ ₂,C₁-C₆ alkyl, C₁-C₄ alkoxy, C₁-C₆ hydroxyalkyl, and C₆-C₁₂ aryl;preferably L¹ is a single covalent bond, or is selected from the groupcomprising C₁-C₁₁ alkylene, C₃-C₁₂ cycloalkylene, and C₆-C₁₂ arylene,with each group being optionally substituted by 1, 2, 3 or 4 groups,either identical or different, selected from the group comprising ahalogen atom, —OH, —CHO, —OCOL¹R⁵, —CO₂R⁶⁰, C₁-C₆ alkyl, and C₆-C₁₂aryl; preferably L¹ is a single covalent bond, or is a C₁-C₁₁ alkylene,or a C₃-C₁₂ cycloalkylene; optionally substituted by 1, 2, or 3 groups,either identical or different, selected from the group comprising ahalogen atom, —OH, —CHO, —OCOL¹R⁵, —CO₂R⁶⁰, C₁-C₆ alkyl, and C₆-C₁₂aryl;

R¹⁰ is H, or is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆-C₁₂ aryl, each group being optionally substituted by oneor several groups (for example 1, 2, 3, or 4), either identical ordifferent, selected from the group comprising a halogen atom, —OH, —CHO,oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂aryl, —OCOR⁸, and —CO₂R⁶⁰; preferably R¹⁰ is H, or is selected from thegroup comprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, witheach group being optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from the group comprising —OH, —CHO,oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂aryl, —OCOR⁸, and —CO₂R⁶⁰; preferably R¹⁰ is H, or is selected from thegroup comprising C₁-C₂₀ alkyl, and C₂-C₂₀ alkenyl, with each group beingoptionally substituted by 1, 2 or 3 groups, either identical ordifferent, selected from the group comprising —OH, —CHO, oxo, —OCOL²R⁵⁰,C₁-C₂ alkoxy, C₁-C₆ alkyl, and —CO₂R⁶⁰; preferably R¹⁰ is H, or isselected from the group comprising C₁-C₁₂ alkyl, and C₂-C₁₂ alkenyl,with each group being optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from —CHO, oxo, C₁-C₆ alkyl, or—OCOL²R⁵⁰;

R²⁰ is H, cyano, a halogen atom, or —CHO, or is selected from the groupcomprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂arylC₁₋₆alkyl, each group being optionally substituted by one or severalgroups (for example 1, 2, 3, or 4), either identical or different,selected from the group comprising a halogen atom, —OH, —CHO, oxo,cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂ aryl,—OCOR⁸, and —CO₂R⁶⁰; preferably R²⁰ is H or —CHO or is selected from thegroup comprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, witheach group being optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from the group comprising —OH, —CHO,oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂aryl, OCOR⁸, and —CO₂R⁶⁰; preferably R²⁰ is H or —CHO, or is selectedfrom the group comprising C₁-C₂₀ alkyl, and C₂-C₂₀ alkenyl, with eachgroup being optionally substituted by 1, 2 or 3 groups, either identicalor different, selected from —OH, oxo, —CHO, —OCOL²R⁵⁰C₁-C₂ alkoxy, orC₁-C₆ alkyl; preferably R²⁰ is H or —CHO, or is selected from the groupcomprising C₁-C₁₂ alkyl, and C₂-C₁₂ alkenyl, with each group beingoptionally substituted by 1, 2 or 3 groups, either identical ordifferent, selected from —CHO, C₁-C₆ alkyl, or —OCOL²R⁵⁰;

R³⁰ is selected from the group comprising epoxy, —OCOR⁸, —CO₂R⁸, C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂ arylC₁₋₆alkyl, each groupbeing optionally substituted by one or several groups (for example 1, 2,3, or 4), either identical or different, selected from the groupcomprising a halogen atom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰;preferably R³⁰ is selected from the group comprising epoxy, C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with each group being optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising —OH, C₁-C₆ alkyl, —CHO, oxo, epoxy, C₁-C₄alkoxy, —OCOL²R⁵⁰, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰; preferably R³⁰ isselected from the group comprising C₁-C₂₀ alkyl, and C₂-C₂₀ alkenyl,with each group being optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from oxo, C₁-C₂ alkoxy, C₁-C₆ alkyl,—CHO, —OCOL²R⁵⁰ or —CO₂R⁶⁰; preferably R³⁰ is selected from the groupcomprising C₁-C₁₂ alkyl, and C₂-C₁₂ alkenyl, with each group beingoptionally substituted by 1, 2 or 3 groups, either identical ordifferent, selected from C₁-C₆ alkyl, —CHO, —OCOL²R⁵⁰, or —CO₂R⁶⁰;

R⁴⁰ is H, cyano, a halogen atom, or —CHO, or is selected from the groupcomprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, each groupbeing optionally substituted by one or several groups (for example 1, 2,3, or 4), either identical or different, selected from the groupcomprising a halogen atom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰;preferably R⁴⁰ is H or —CHO, or is selected from the group comprisingC₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with each group beingoptionally substituted by 1, 2 or 3 groups, either identical ordifferent, selected from the group comprising —OH, oxo, epoxy, C₁-C₄alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOL²R⁵⁰, and —CO₂R⁶⁰; preferably R⁴⁰is H or —CHO, or is selected from the group comprising C₁-C₂₀ alkyl, andC₂-C₂₀ alkenyl, with each group being optionally substituted by 1, 2 or3 groups, either identical or different, selected from the groupcomprising oxo, C₁-C₂ alkoxy, C₁-C₆ alkyl, —OCOL²R⁵⁰, and —CO₂R⁶⁰;preferably R⁴⁰ is H or —CHO, or is selected from the group comprisingC₁-C₁₂ alkyl, and C₂-C₁₂ alkenyl, with each group being optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom C₁-C₆ alkyl, —OCOL²R⁵⁰, or —CO₂R⁶⁰; preferably R⁴⁰ is H, —CHO orC₁-C₁₂ alkyl, optionally substituted by 1, 2 or 3 groups, eitheridentical or different, selected from C₁-C₆ alkyl, —OCOL²R⁵⁰, or—CO₂R⁶⁰; preferably R⁴⁰ is H or —CHO; or R¹⁰ and R³⁰ may, with thecarbons to which they are bound, form a group selected from a C₅-C₁₂cycloalkyl or a C₅-C₁₂ cycloalkenyl, each group being optionallysubstituted by one or several groups (for example 1, 2, 3, or 4), eitheridentical or different, selected from the group comprising a halogenatom, —OH, —CHO, cyano, oxo, epoxy, —OCOR⁸, —CO₂R⁶⁰, —OCOL²R⁵⁰, C₁-C₆alkyl, C₁-C₆ hydroxyalkyl, and C₂-C₆ alkenyl; or else R¹⁰ and R³⁰ maypreferably, with the carbons to which they are bound, form a groupselected from a C₅-C₁₂ cycloalkyl or a C₅-C₁₂ cycloalkenyl, with eachgroup being optionally substituted by 1, 2, 3 or 4 groups, eitheridentical or different, selected from the group comprising —OH, —CHO,oxo, epoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, and C₂-C₆ alkenyl; preferably R¹⁰and R³⁰ may, with the carbons to which they are bound, form a groupselected from a C₅-C₁₀ cycloalkyl or a C₅-C₁₀ cycloalkenyl, with eachgroup being optionally substituted by 1, 2 or 3 groups, either identicalor different, selected from the group comprising —OH, —CHO, epoxy, C₁-C₆alkyl, and C₂-C₆ alkenyl;

R⁵⁰ is selected from the group comprising H, —CHO, epoxy, a halogenatom, —OH, cyano, nitro, isocyanate, C₁-C₂₀ alkyl, C₁-C₄ alkoxy, C₂-C₂₀alkenyl, C₂-C₂₀ alkynyl, heterocycloalkyl, —CO₂R⁸, and —NR⁹ ₂;preferably R⁵⁰ is selected from the group comprising Cl, F, I, Br, —OH,—CHO, epoxy, —SH, cyano, nitro, isocyanate, C₁-C₄ alkoxy, C₂-C₁₂alkenyl, C₂-C₁₂ alkynyl, heterocycloalkyl, —CO₂R⁸, and —NR⁹ ₂;preferably, R⁵⁰ is selected from the group comprising Cl, F, I, Br, —OH,—CHO, —SH, cyano, and nitro, preferably —OH, —CHO, —SH, epoxy, cyano ornitro, preferably —OH, —SH or cyano;

L² is a single covalent bond, or is selected from the group comprisingC₁-C₂₀ alkylene, C₃-C₁₂ cycloalkylene, C₂-C₁₂ alkenylene, C₅-C₁₂cycloalkenylene, C₆-C₁₂ arylene, heteroarylene, and heterocycloalkylene,each group being optionally substituted by one or several groups (forexample 1, 2, 3, or 4), either identical or different, selected from thegroup comprising a halogen atom, oxo, nitro, —CHO, —OH, —NR⁹ ₂, C₁-C₆alkyl, C₁-C₄ alkoxy, C₆-C₁₂ arylC₁₋₆alkyl, C₁₋₆ alkylC₆-C₁₂aryl, C₆-C₁₂aryloxy, C₁-C₆ hydroxyalkyl, and C₆-C₁₂ aryl; preferably L² is a singlecovalent bond, or is selected from the group comprising C₁-C₂₀ alkylene,C₃-C₁₂ cycloalkylene, C₅-C₁₂ cycloalkenylene, and C₆-C₁₂ arylene, witheach group being optionally substituted by 1, 2, 3 or 4 groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, —CHO, nitro, —CO₂R⁶⁰, —NR⁹ ₂, C₁-C₆ alkyl, C₁-C₄ alkoxy,C₁-C₆ hydroxyalkyl, and C₆-C₁₂ aryl; preferably L² is a single covalentbond, or is selected from the group comprising C₁-C₁₁ alkylene, C₃-C₁₂cycloalkylene, and C₆-C₁₂ arylene, with each group being optionallysubstituted by 1, 2, 3 or 4 groups, either identical or different,selected from the group comprising a halogen atom, —OH, —CHO, —CO₂R⁶⁰,C₁-C₆ alkyl, and C₆-C₁₂ aryl; preferably L² is a single covalent bond,or is a C₁-C₁₁ alkylene, or a C₃-C₁₂ cycloalkylene; optionally replacedby 1, 2 or 3 groups, either identical or different, chosen from thegroup comprising a halogen atom, —OH, —CHO, —CO₂R⁶⁰, C₁-C₆ alkyl, andC₆-C₁₂ aryl;

R⁶⁰ is selected from the groups comprising H or C₁-C₆ alkyl optionallysubstituted by one or several groups (for example 1, 2, 3, or 4), eitheridentical or different, chosen from the group comprising —OH, —CHO,—O—COR⁷, and C₁-C₆ alkyl; preferably R⁶⁰ is selected from the groupscomprising H or C₁-C₄ alkyl, optionally substituted by 1, 2 or 3 groups,either identical or different, selected from the group comprising —OH,—CHO, —O—COR⁷, and C₁-C₄ alkyl;

R⁷ is selected from the group comprising C₁-C₂₄ alkyl, C₂-C₂₀ alkenyl,and C₆-C₁₂ aryl, with each group being optionally substituted by one orseveral groups, either identical or different, chosen from the groupcomprising —OH, epoxy and —OCOL¹R⁵; R⁷ is preferably selected from thegroup comprising C₄-C₂₄ alkyl, C₄-C₂₀ alkenyl, and C₆-C₁₂ aryl, witheach group being optionally substituted by 1, 2 or 3 identical ordifferent groups, selected from —OH, epoxy, or —OCOL¹R⁵;

R⁷ is preferably selected from the group comprising C₆-C₂₄ alkyl, andC₆-C₂₀ alkenyl, with each group being optionally substituted by 1, 2 or3 identical or different groups, selected from —OH, epoxy, or —OCOL¹R⁵;preferably R⁷ is selected from the group comprising C₁₀-C₂₄ alkyl, andC₁₀-C₂₀ alkenyl, with each group being optionally substituted by 1, 2 or3 identical or different groups, selected from —OH, epoxy, or —OCOL¹R⁵;R⁷ is preferably selected from the group comprising C₁₈-C₂₄ alkyl, andC₁₈-C₂₀ alkenyl, with each group being optionally substituted by 1, 2 or3 identical or different groups, selected from —OH, epoxy, or —OCOL¹R⁵;

R⁸ is selected from H or C₁-C₆ alkyl; preferably R⁸ is selected from Hor C₁-C₄ alkyl; preferably R⁸ is selected from H or C₁-C₂ alkyl; andeach identical or different R⁹ is selected from H, C₁-C₆ alkyl, orC₆-C₁₂ aryl, preferably each identical or different R⁹ is selected fromH or C₁-C₄ alkyl; preferably each identical or different R⁹ is selectedfrom H or C₁-C₂ alkyl.

The term “C₁-C₂₀ alkyl” refers to a linear or branched, saturatedhydrocarbon radical, comprising from 1 to 20 carbon atoms, such asmethyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl oricosyl.

The term “C₁-C₂₀ alkenyl” refers to a linear or branched hydrocarbonradical, comprising one or several double bonds, having from 2 to 20carbon atoms. Branched means that one or several lower alkyl groups,such as methyl, ethyl or propyl, are bound to a linear alkenyl chain. Byway of example of a C₁-C₂₀ alkenyl one may cite the ethenyl group,1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl,3-methyl-3-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl,3-heptenyl, 1-octenyl, 4-octenyl, 4-nonenyl, 5-decenyl, 5-undecenyl,6-dodecenyl, tetradecenyl, 9-hexadecenyl, 9-octadecenyl, 13-docosaenyl,15-tetracosaenyl, 9, 12-octadecadienyl, 9,12,15-octadecatrienyl,6,9,12-octadecatrienyl, 8,11,14-eicosatrienyl,5,8,11,14-eicosatetraenyl, 5,8,11,14,17-eicosapentaenyl, and4,7,10,13,16,19-docosahexaenoyl.

The term “C₅-C₁₂ cycloalkyl” refers to a saturated mono- or polycyclichydrocarbon radical, having from 5 to 12 carbon atoms. By way of exampleof a monocyclic cycloalkyl, one may cite for example cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl. Byway of example of a polycyclic cycloalkyl group, one may cite inparticular 1-decaline, norbornyl, or adamant-(1 or 2-)yl.

The term “C₅-C₁₂ cycloalkenyl” refers to a group derived from acycloalkyl group, as defined above, presenting one or several doublebonds. For example, this could be the cyclopentenyl group, cyclohexenyl,cyclopenta-1,3-dienyl, cycloheptenyl, cyclooctenyl,cycloocta-1,4-dienyl, cyclodecenyl, cyclodeca-1,5-dienyl.

The term “C₂-C₂₀ alkynyl” refers to a linear or branched hydrocarbonchain comprising one or several trible bonds. Branched means that one orseveral lower alkyl groups, such as methyl, ethyl or propyl, are boundto a linear alkynyl chain. Examples of alkynyl groups are in particularthe groups ethynyl, 1-propynyl, 1-butynyl, 2-butynyl, etc.

The term “C₆-C₁₂ aryl” refers to an aromatic monocyclic or polycyclichydrocarbon radical, having 6 to 12 atoms of carbon, more preferably 6carbon atoms. The aryl groups include in particular include the phenyl,naphtyl and biphenyl groups.

The term “C₁₋₆ alkylC₆-C₁₂aryl” refers to an aryl group substituted byat least one C₁-C₆ alkyl group, with the aryl and alkyl groups being asdefined above.

The term “C₆-C₁₂ arylC₁₋₆alkyl” or “aralkyl” refers to an alkyl groupsubstituted by at least one C₆-C₁₂ aryl group, with the aryl and alkylgroups being as defined above. As an example of aralkyl groups, one mayconsider in particular benzyl, 2-phenethyl and naphthalenemethyl.

The term “C₁-C₄ alkoxy” refers to an alkyl-O— group in which the alkylterm has the meaning given above. Examples of C₁-C₄ alkoxy groups arethe methoxy, ethoxy, propoxy, and butoxy groups.

The term “C₆-C₁₂ aryloxy” refers to an aryl-O— group in which the arylterm has the meaning given above. An example of a C₆-C₁₂ aryloxy groupis phenoxy.

The term “heterocycloalkyl” refers to mono-, bi- or poly-cyclichydrocarbon systems, saturated or unsaturated, presenting at least oneheteroatom on the cycle(s), such as nitrogen, sulfur or oxygen. They arenon-aromatic. For the heterocycle, one can cite in particular thepiperidine group, piperazine, pyrrolidine, pyrrolidinone, morpholine,phthalane, phthalide, thiazolidinedione, sulfolane, benzo[1,3]dioxolane,benzo[1,4]dioxane, [2,3]dihydrobenzofurane, quinazolinone,benzothiadiazinone, 1-methyl-piperidin-4-yl or1-methyl-piperidin-4-ylmethyl.

The term “heteroaryl” refers to one or several aromatic unsaturatedcycles comprising one or several heteroatoms, either identical ordifferent, selected from N, O and S, such as the pyridinyl, pyrimidinyl,furyl, thienyl, benzothienyl, oxazolyl, benzoxazolyl, isoxazolyl,thiazolyl, pyrolyl, pyrazolyl, imidazolyl, triazolyl, and tetrazolylgroups.

The term “C₁-C₁₁ alkylene” refers to a linear or branched, saturated,divalent alkyl group. Examples of alkylene groups are, in particular,the methylene, ethylene, 1-methyl ethylene, propylene, etc. groups.

The term “C₂-C₁₂ alkenylene” refers to a divalent alkenyl group, withthe alkenyl group being as defined above.

The term “C₃-C₁₂ cycloalkylene” refers to a divalent cycloalkyl group,with the cycloalkyl group being as defined above.

The term “C₆-C₁₂ arylene” refers to a divalent aryl group, with the arylgroup being as defined above.

The term “heterocycloalkylene” refers to a divalent heterocycloalkylgroup, with the heterocycloalkyl group being as defined above.

The term “heteroarylene” refers to a divalent heteroarylene group, withthe heteroarylene group being as defined above.

The term “hydroxyalkyl” designates groups in which the alkyl group is asdefined above, and in which at least one carbon atom is substituted by ahydroxyl radical, for example hydroxymethyl, hydroxyethyl,2-hydroxy-butyl.

The term “halogen” or “halogen atom” refers to a chlorine, bromine,fluorine or iodine atom.

The term “oxo” refers to a ═O group.

The term “cyano” refers to a —C≡N group.

The term “epoxy” refers to a

group.

The term “polymer” is understood to mean a molecule of formula (Ic) or(Id),

where p is repeated a large number of times (up to several thousands).For example, p is a whole number comprised between 1 and 10,000,preferably p is a whole number comprised between 1 and 1,000, forexample p is a whole number comprised between 1 and 100. Preferably thepolymer of the compound of formula (Ia) or (Ib) is an oligomer.“Oligomer” is understood to mean a molecule of formula (Ic) or (Id) inwhich p is repeated less than 20 times (p is a whole number less than20).

The foregoing definitions are applicable to the description, theexamples and the claims of the invention. In order to facilitateunderstanding, the nomenclature of groups, reagents, solvents andproducts is the international nomenclature or the nomenclature commonlyused by a person skilled in the art.

According to a preferred embodiment, the invention relates to a processof synthesizing compounds of the family represented by formula (Ia) or(Ib), a stereoisomer, a mix of compounds belonging to this family,and/or an oligomer and/or a polymer thereof, wherein:

R¹ is H or is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆-C₁₂ aryl, with each group being optionally substitutedby 1, 2 or 3 groups, either identical or different, selected from thegroup comprising —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy,C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOL¹R⁵, —OCOR⁸, and —CO₂R⁶⁰;

R² is H or is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂ arylC₁₋₆alkyl, with each group beingoptionally substituted by 1, 2 or 3 groups, either identical ordifferent, selected from the group comprising —OH, —CHO, epoxy, oxo,cyano, —NR⁹ ₂, C₁-C₄ alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOL¹R⁵, —OCOR⁸,and —CO₂R⁶⁰;

R³ is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl,and C₆-C₁₂ aryl, with each group being optionally substituted by 1, 2 or3 groups, either identical or different, selected from the groupcomprising —OH, —CHO, oxo, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl, C₆-C₁₂aryl, —OCOL¹R⁵ and —CO₂R⁶⁰;

R⁴ is H, or is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆-C₁₂ aryl, with each group being optionally substitutedby 1, 2 or 3 groups, either identical or different, selected from thegroup comprising —OH, —CHO, oxo, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl,C₆-C₁₂ aryl, —OCOL¹R⁵, and —CO₂R⁶⁰;

or R¹ and R³ may, with the carbons to which they are bound, form a groupselected from a C₅-C₁₂ cycloalkyl or a C₅-C₁₂ cycloalkenyl, with eachgroup being optionally substituted by 1, 2, 3 or 4 groups, eitheridentical or different, selected from the group comprising an —OH, oxo,epoxy, —OCOL¹R⁵, —OCOR⁸, —CO₂R⁶⁰, C₁-C₆ alkyl, and C₂-C₆ alkenyl;

R⁵ is selected from the group comprising Cl, F, I, Br, —OH, —SH, —CHO,epoxy, cyano, nitro, isocyanate, C₁-C₄ alkoxy, C₂-C₁₂ alkenyl, C₂-C₁₂alkynyl, heterocycloalkyl, —CO₂R⁸, and —NR⁹ ₂;

R⁶ is H or —CO-L¹-R⁵;

L¹ is a single covalent bond, or is selected from the group comprisingC₁-C₂₀ alkylene, C₃-C₁₂ cycloalkylene, C₅-C₁₂ cycloalkenylene, andC₆-C₁₂ arylene, with each group being optionally substituted by 1, 2, 3or 4 groups, either identical or different, selected from the groupcomprising a halogen atom, —OH, oxo, —CHO, —OCOL¹R⁵, —CO₂R⁶⁰, C₁-C₆alkyl, C₁-C₄ alkoxy, C₁-C₆ hydroxyalkyl, and C₆-C₁₂ aryl;

R⁶⁰ is selected from the groups comprising H and C₁-C₄ alkyl optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising —OH, —CHO, —O—COR⁷, and C₁-C₄ alkyl;

R⁷ is selected from the group comprising C₄-C₂₄ alkyl, C₄-C₂₀ alkenyl,and C₆-C₁₂ aryl, with each group being optionally substituted by 1, 2 or3 identical or different groups, chosen from the group comprising —OH,epoxy and —OCOL¹R⁵;

R⁸ is selected from H or C₁-C₄ alkyl; and each identical or different R⁹is selected from H or C₁-C₄ alkyl.

According to a preferred embodiment, the invention concerns a processfor the synthesis of compounds of the family represented by formula (Ia)or (Ib), a stereoisomer, a combination of compounds of this family,and/or an oligomer and/or a polymer thereof, wherein:

R¹ is H or is selected from the group comprising C₁-C₂₀ alkyl, andC₂-C₂₀ alkenyl, with each group being optionally substituted by 1, 2 or3 groups, either identical or different, selected from the groupcomprising —OH, oxo, C₁-C₂ alkoxy, C₁-C₆ alkyl, —OCOL¹R⁵, and —CO₂R⁶⁰;

R² is H or is selected from the group comprising C₁-C₂₀ alkyl, andC₂-C₂₀ alkenyl, with each group being optionally substituted by 1, 2 or3 groups, either identical or different, selected from the groupcomprising oxo, C₁-C₂ alkoxy, C₁-C₆ alkyl, —OCOL¹R⁵, and —CO₂R⁶⁰;

R³ is selected from the group comprising C₁-C₂₀ alkyl, and C₂-C₂₀alkenyl, with each group being optionally substituted by 1, 2 or 3groups, either identical or different, selected from the groupcomprising —OH, oxo, C₁-C₂ alkoxy, C₁-C₆ alkyl, —OCOL¹R⁵ and —CO₂R⁶⁰;

R⁴ is H, or is selected from the group comprising C₁-C₂₀ alkyl, andC₂-C₂₀ alkenyl, with each group being optionally substituted by 1, 2 or3 groups, either identical or different, selected from the groupcomprising oxo, C₁-C₂ alkoxy, C₁-C₆ alkyl, —OCOL¹R⁵, and —CO₂R⁶⁰;

or R¹ and R³ may, with the carbons to which they are bound, form a groupselected from a C₅-C₁₀ cycloalkyl and a C₅-C₁₀ cycloalkenyl, with eachgroup being optionally substituted by 1, 2 or 3 groups, either identicalor different, chosen from the group comprising —OH, epoxy, C₁-C₆ alkyl,and C₂-C₆ alkenyl;

R⁵ is selected from the group comprising Cl, F, I, Br, —OH, —CHO, epoxy,—SH, cyano, and nitro, preferably —OH, —SH, epoxy, cyano, and nitro,preferably —OH, —SH, epoxy, or cyano;

R⁶ is H or —CO-L¹-R⁵;

L¹ is a single covalent bond, or is selected from the group comprisingC₁-C₁₁ alkylene, C₃-C₁₂ cycloalkylene, and C₆-C₁₂ arylene, with eachgroup being optionally substituted by 1, 2, 3 or 4 groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, —CHO, —OCOL¹R⁵, —CO₂R⁶⁰, C₁-C₆ alkyl, and C₆-C₁₂ aryl;

R⁶⁰ is selected from the group comprising H and C₁-C₄ alkyl optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising —OH, —CHO, —O—COR⁷, and C₁-C₄ alkyl;

R⁷ is selected from the group comprising C₆-C₂₄ alkyl, and C₆-C₂₀alkenyl, with each group being optionally substituted by 1, 2 or 3groups, either identical or different, selected from the groupcomprising —OH, epoxy and —OCOL¹R⁵;

R⁸ is selected from H or C₁-C₄ alkyl; and each R⁹ that is identical ordifferent is selected from H or C₁-C₄ alkyl.

The invention therefore relates to a process for the preparation ofcompounds of formula (Ia), (Ib), (Ic) or (Id), or a combination thereof,since said procedure includes the reaction of at least one unsaturatedmolecule of formula (II) with atmospheric or molecular oxygen, in thepresence of at least one aldehyde of formula (III), and optionally inthe presence of at least one catalyst or at least one radical initiator.According to a particular embodiment, the unsaturated molecule offormula (II) may be the same molecule as the aldehyde of formula (III).

According to a particular embodiment, the process comprises the reactionof an unsaturated molecule of formula (II) with atmospheric or molecularoxygen, in the presence of at least one aldehyde of formula (III) andoptionally in the presence of at least one catalyst or at least oneradical initiator, wherein:

R¹⁰ is H, or is selected from the group comprising C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆-C₁₂ aryl, with each group being optionally substitutedby 1, 2 or 3 groups, either identical or different, selected from thegroup comprising —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy,—OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰;

R²⁰ is H or —CHO or is selected from the group comprising C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with each group being optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂ aryl, OCOR⁸, and —CO₂R⁶⁰;

R³⁰ is selected from the group comprising epoxy, C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆-C₁₂ aryl, with each group being optionally substitutedby 1, 2 or 3 groups, either identical or different, selected from thegroup comprising —OH, C₁-C₆ alkyl, —CHO, oxo, epoxy, C₁-C₄ alkoxy,—OCOL²R⁵⁰, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰;

R⁴⁰ is H or —CHO, or is selected from the group comprising C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with each group being optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising —OH, oxo, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl,C₆-C₁₂ aryl, —OCOL²R⁵⁰, and —CO₂R⁶⁰;

or R¹⁰ and R³⁰ may, with the carbons to which they are bound, form agroup selected from a C₅-C₁₂ cycloalkyl or a C₅-C₁₂ cycloalkenyl, witheach group being optionally substituted by 1, 2, 3 or 4 groups, eitheridentical or different, selected from the group comprising —OH, —CHO,oxo, epoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, and C₂-C₆ alkenyl;

R⁵⁰ is selected from the group comprising Cl, F, I, Br, —OH, —CHO,epoxy, —SH, cyano, nitro, isocyanate, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl,heterocycloalkyl, —CO₂R⁸, and —NR⁹ ₂;

L² is a single covalent bond, or is selected from the group comprisingC₁-C₂₀ alkylene, C₃-C₁₂ cycloalkylene, C₅-C₁₂ cycloalkenylene, andC₆-C₁₂ arylene, with each group being optionally substituted by 1, 2, 3or 4 groups, either identical or different, selected from the groupcomprising a halogen atom, —OH, —CHO, nitro, —CO₂R⁶⁰, —NR⁹ ₂, C₁-C₆alkyl, C₁-C₄ alkoxy, C₁-C₆ hydroxyalkyl, and C₆-C₁₂ aryl;

R⁶⁰ is selected from the groups comprising H and C₁-C₄ alkyl, optionallysubstituted by 1, 2 or 3 identical or different groups, selected fromthe group comprising —OH, —CHO, —O—COR⁷, and C₁-C₄ alkyl;

R⁷ is selected from the group comprising C₄-C₂₄ alkyl, C₄-C₂₀ alkenyl,and C₆-C₁₂ aryl, with each group being optionally substituted by 1, 2,or 3 groups, either identical or different, selected from the groupcomprising —OH, epoxy, and —OCOL¹R⁵;

R⁸ is selected from H or C₁-C₄ alkyl; and

each identical or different R⁹ is selected from H or C₁-C₄ alkyl.

According to a preferred embodiment, the process comprises the reactionof an unsaturated molecule of formula (II) with atmospheric or molecularoxygen, in the presence of at least one aldehyde of formula (III) andoptionally in the presence of at least one catalyst, or at least oneradical initiator, wherein:

R¹⁰ is H, or is selected from the group comprising C₁-C₂₀ alkyl, andC₂-C₂₀ alkenyl, with each group being optionally substituted by 1, 2 or3 groups, either identical or different, selected from the groupcomprising —OH, —CHO, oxo, —OCOL²R⁵⁰, C₁-C₂ alkoxy, and C₁-C₆ alkyl;

R²⁰ is H or —CHO, or is selected from the group comprising C₁-C₂₀ alkyl,and C₂-C₂₀ alkenyl, with each group being optionally substituted by 1, 2or 3 groups, either identical or different, selected from the groupcomprising —OH, oxo, —CHO, —OCOL²R⁵⁰, C₁-C₂ alkoxy, and C₁-C₆ alkyl;

R³⁰ is selected from the group comprising C₁-C₂₀ alkyl, and C₂-C₂₀alkenyl, with each group being optionally substituted by 1, 2 or 3groups, either identical or different, selected from the groupcomprising oxo, C₁-C₂ alkoxy, C₁-C₆ alkyl, —CHO, —OCOL²R⁵⁰ and —CO₂R⁶⁰;

R⁴⁰ is H or —CHO, or is selected from the group comprising C₁-C₂₀ alkyl,and C₂-C₂₀ alkenyl, with each group being optionally substituted by 1, 2or 3 groups, either identical or different, selected from C₁-C₂ oxoalkoxy, C₁-C₆ alkyl, —OCOL²R⁵⁰, or —CO₂R⁶⁰; or R¹⁰ and R³⁰ may, with thecarbons to which they are bound, form a group selected from a C₅-C₁₀cycloalkyl or a C₅-C₁₀ cycloalkenyl with each group being optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising —OH, —CHO, epoxy, C₁-C₆ alkyl, and C₂-C₆alkenyl;

R⁵⁰ is selected from the group comprising Cl, F, I, Br, —OH, —CHO,epoxy, —SH, cyano, and nitro;

L² is a single covalent bond, or is selected from the group comprisingC₁-C₁₁ alkylene, C₃-C₁₂ cycloalkylene, and C₆-C₁₂ arylene, with eachgroup being optionally substituted by 1, 2, 3 or 4 groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, nitro, —CHO, —CO₂R⁶⁰, C₁-C₆ alkyl, and C₆-C₁₂ aryl;

R⁶⁰ is selected from the groups comprising H and C₁-C₄ alkyl optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising —OH, —CHO, —O—COR⁷, and C₁-C₄ alkyl;

R⁷ is selected from the group comprising C₆-C₂₄ alkyl, and C₆-C₂₀alkenyl, with each group being optionally substituted by 1 or 2 groups,either identical or different, selected from the group comprising —OH,epoxy and —OCOL¹R⁵;

R⁸ is selected from H or C₁-C₄ alkyl; and each identical or different R⁹is selected from H or C₁-C₄ alkyl.

According to one particular embodiment, the process may be carried outat atmospheric pressure. According to another particular embodiment, theprocess may be carried out under pressure or under a constant flow ofoxygen or of air. The oxygen flow rate may be controlled, for example bya flow meter. Advantageously, the reaction medium is kept at saturationwith dissolved oxygen.

According to a particular embodiment, the process comprises the reactionof at least one saturated molecule of formula (II) with atmospheric ormolecular oxygen, in the presence of at least one aldehyde of formula(III).

According to another particular embodiment, the process comprises thereaction of at least one unsaturated molecule of formula (II) withatmospheric or molecular oxygen, in the presence of at least onealdehyde of formula (III), and in the presence of at least one catalystor in the presence of at least one radical initiator, such asazobisisobutyronitrile (AIBN), azobiscyanocyclohexane (ACHN) orazobis(4-cyanopentanoic) acid (ACVA). According to a preferredembodiment, the reaction is conducted in the presence of a catalyst,preferably a solid catalyst.

According to this embodiment, the process is a heterogeneous catalyticprocess. Therefore the catalyst is not consumed in the reaction and isnot dissolved in the reaction medium. Since it remains in solid form, itis easy to separate it from the reaction medium with no loss of thecatalyst and without pollution of the reaction medium by dissolvedspecies or catalyst residue. The solid catalyst may be eliminated bysimple filtration or immobilization in a catalyst bed allowing it to berecycled in both cases.

Preferably, the bulk or supported catalyst is a catalyst based on ametal from Groups 6 through 12 of the periodic table of elements and onecan preferably cite catalysts based on ruthenium, palladium, platinum,cobalt, manganese, nickel, copper, zinc or iron, deposited for exampleon a solid support such as aluminas, activated carbons, oxides of zinc,of magnesium and of titanium, silicas, zeolites or polymeric resins.According to a particular embodiment, the catalyst is selected from thegroup comprising catalysts based on ruthenium, palladium, platinum,cobalt, manganese, nickel, copper, zinc or iron or activated carbon.According to a preferred embodiment, the catalyst is based on ruthenium,supported nickel or cobalt, or activated carbon. The catalyst ispreferably a catalyst based on ruthenium or supported cobalt.

According to a preferred embodiment, the catalyst is based on rutheniumsupported on silica prepared from ruthenium chloride and a colloidalsilica suspension.

According to another preferred embodiment, the catalyst is a catalystbased on supported nickel, for example a catalyst based on nickelsupported on activated carbon.

The catalyst may be introduced into the reaction at a ratio of 0 to 10%by weight of the quantity of unsaturated molecules engaged, for examplefrom 0.1 to 10%, preferably at a ratio of 0.1 to 8%, preferably at aratio of 0.1 to 5%, Advantageously from 0.5 to 3%, preferably at a ratioof 0.5 to 1%.

According to a particular embodiment, the compound of formula (II) maybe a C₃-C₂₀ alkene or a C₅-C₁₂ cycloalkene, with each alkene orcycloalkene being optionally substituted by one or several groups,either identical or different, selected from the group comprising ahalogen atom, —CHO, —OH, cyano, oxo, epoxy, —OCOR⁸, C₁-C₆ alkyl, C₂-C₆alkenyl, C₆-C₁₂ aryl, —OCOL²R⁵⁰, and —CO₂R⁶⁰; with each alkyl, alkenyl,or aryl being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, oxo, —CHO, —OH, C₁-C₆ alkyl, C₆-C₁₂ aryl —OCOL²R⁵⁰, —OCOR⁸, and—CO₂R⁶⁰.

According to a particular embodiment, the compound of formula (II) isselected from the group comprising 1-pentene, 1-hexene, 1-heptene,1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-octadecene,1-nonadecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene,3-butene-1,2-diol, 2-butene-1,4-diol, 2-bromo-2-butene,1,4-dichloro-2-butene, 2,3-dimethyl-2-butene, 2-chloro-2-butene,3,4-epoxy-1-butene, 1,1-diacetoxy-2-butene,2,3-dibromo-2-butene-1,4-diol, 1-chloro-2-butene, 2-methyl-3-buten-2-ol,3-buten-2-ol, 3-buten-2-one, 3-butenenitrile,2,3-dimethyl-1,3-butadiene, 2-pentene, 2,4,4-trimethyl-2-pentene,2-methyl-2-pentene, 3-ethyl-2-pentene, 5-o-tolyl-2-pentene,4-methyl-2-pentene, 1-penten-3-ol, 3-methyl-3-penten-2-one,4-methyl-3-penten-2-one, 2-hexene, 1,2-epoxy-5-hexene,3,4-bis(4-hydroxyphenyl)-3-hexene, 5-hexen-2-one, 3-hexen-1-ol,cyclohexene, 3-cyclohexene-1-carboxaldehyde, 3-cyclohexene-1-methanol,4-vinyl-1-cyclohexene, cyclohexene-1-carbonitrile,1-cyclohexenylacetonitrile, p-mentha-1,8-diene (limonene),p-mentha-1,8-diene-7-ol, 1,4-cyclohexadiene,1-isopropyl-4-methyl-1,3-cyclohexadiene (terpinene), p-benzoquinone,6-methyl-5-hepten-2-one, bicyclo[2.2.1]hept-2-ene (norbornene),(1r,5r)-2,6,6-trimethylbicyclo[3.1.1]hept-2-ene (pinene), 4-octene,1,7-octadiene, 1-octen-3-yl acetate, cyclooctene, cyclooctadiene,4-nonene, 10-undecen-1-ol, 7-tetradecene, 1,7-hexadecadiene,1-amino-9-octadecene (oleylamine), ethyl acrylate, ethyl methacrylate,isoprene, myrcene, styrene, [alpha]-methylstyrene, vinyl acetate. Forexample, the compound of formula (II) is selected from the groupcomprising 1-octene, 3-butenenitrile, 2,3-dimethyl-1,3-butadiene,2-hexene, 3-hexen-1-01, cyclohexene, 3-cyclohexene-1-carboxaldehyde,1-cyclohexenylacetonitrile, p-mentha-1,8-diene (limonene),1-isopropyl-4-methyl-1,3-cyclohexadiene (terpinene),6-methyl-5-hepten-2-one, bicyclo[2.2.1]hept-2-ene (norbornene),(1r,5r)-2,6,6-trimethylbicyclo[3.1.1]hept-2-ene (pinene), 4-octene,cyclooctene, cyclooctadiene, 4-nonene, ethyl acrylate, ethylmethacrylate, isoprene, myrcene, styrene, [alpha]-methylstyrene. Forexample, the compound of formula (II) is selected from the groupcomprising 1-octene, 2-hexene, cyclohexene,3-cyclohexene-1-carboxaldehyde, 1-cyclohexenylacetonitrile,p-mentha-1,8-diene (limonene), 6-methyl-5-hepten-2-one,bicyclo[2.2.1]hept-2-ene (norbornene),(1r,5r)-2,6,6-trimethylbicyclo[3.1.1]hept-2-ene (pinene), 4-octene,cyclooctene, cyclooctadiene, myrcene, styrene, and[alpha]-methylstyrene. For example, the compound of formula (II) isselected from the group comprising cyclohexene, 4-octene, cyclooctene,cyclooctadiene, myrcene, and styrene.

According to a particular embodiment, the compound of formula (II) is anunsaturated fatty body, preferably having the formulaR¹⁰CH═CH—(CH₂)_(u)—CO₂R⁶⁰ in which u is a whole number comprised between2 and 11, preferably selected from 2, 3, 4, 5, 6, 7, 8, 9, or 10, andR¹⁰ and R⁶⁰ have the same meaning as above.

The term “unsaturated fatty body” is used generically and it alsodesignates unsaturated fatty acids per se, alone or in combination withsaturated fatty acids, as well as their by-products, i.e. their C₁-C₆ester alkylic, or glyceric form, as mono-, di- or triglycerides, orglycolic and/or mixtures thereof. The concept of “unsaturated fattyacid” within the meaning of the present description includesspecifically the unsaturated compounds present in plant and animal oilsand esters of fatty acids contained in these oils, as well as thecorresponding fatty acids (non-sterified carboxylic acids). As examplesof unsaturated fatty acids that may be used in the present invention,one may cite unsaturated fatty acids presenting a single double bondsuch as the following acids: linderic, myristoleic, palmitoleic, oleic,petroselenic, doeglic, gadoleic, erucic acids; unsaturated fatty acidspresenting two double bonds such as linoleic acid; unsaturated fattyacids presenting 3 double bonds, such as linolenic acid; unsaturatedfatty acids presenting more than 4 double bonds, such as isanic,stearodonic, arachidonic, chypanodonic acids; unsaturated fatty acidscontaining a hydroxyl group, such as ricinoleic acid, their C₁-C₆alkylic ester, or their mono-, di- or triglyceride form, or acombination thereof. According to a particular embodiment, unsaturatedfatty acids are selected from the group comprising undecylenic acid (Δ⁹undecylenic), lauroleic acid (Δ⁹ dodecenoic), myristoleic acid (Δ⁹tetradecenoic), palmitoleic acid (Δ⁹ hexacedecenoic), petroselinic acid(Δ⁶ octadecenoic), oleic acid (Δ^(9c) octadecenoic), elaidic (Δ^(9t)octadecenoic), vaccenic acid (Δ^(11t) octadecenoic), ricinoleic acid(OH¹²,Δ^(9t) octadecenoic), linoleic acid (Δ^(9c),Δ^(12c)octadecadienoic), linolenic acid (Δ^(9c),Δ^(12c),Δ^(15c)octadecatrienoic), gondoic acid (Δ¹¹ eicosenoic), erucic acid (Δ¹³docosenoic), vernolic acid (12, 13-epoxy-9-cis-octadecenoic), coronoricacid (9,10-epoxy-12-cis-octadecenoic), alchornoic acid(14,15-epoxy-11-cis-eicosanoic) their C₁-C₆ alkylic ester or theirmono-, di- or triglyceride form, or a combination thereof. According toa particular embodiment, unsaturated fatty acids are selected from thegroup comprising undecylenic acid (Δ⁹ undecylenic), lauroleic acid (Δ⁹dodecenoic), myristoleic acid (Δ⁹ tetradecenoic), palmitoleic acid (Δ⁹hexacedecenoic), oleic acid (Δ^(9c) octadecenoic), elaidic acid (Δ^(9t)octadecenoic), vaccenic acid (Δ^(11t) octadecenoic), ricinoleic acid(OH¹²,Δ^(9t) octadecenoic), linoleic acid (Δ^(9c),Δ^(12c)octadecadienoic), linolenic acid (Δ^(9c),Δ^(2c),Δ^(5c)octadecatrienoic), erucic acid (Δ¹³ docosenoic), vernolic acid(12,13-epoxy-9-cis-octadecenoic), their C₁-C₆ alkylic ester or theirmono-, di- or triglyceride form, or a combination thereof. According toa particular embodiment, the unsaturated fatty acids are selected fromthe group comprising lauroleic acid (Δ⁹ dodecenoic), palmitoleic acid(Δ⁹ hexacedecenoic), oleic acid (Δ^(9c) octadecenoic), ricinoleic acid(OH¹²,Δ^(9t) octadecenoic), linoleic acid (Δ^(9c),Δ^(12c),octadecadienoic), linolenic acid (Δ^(9c),Δ^(12c),Δ^(15c)octadecatrienoic), their C₁-C₆ alkalic ester, or their mono-, di- ortriglyceride form, or a combination thereof. According to a particularembodiment, the unsaturated fatty acids are selected from the groupcomprising oleic acid (Δ^(9c) octadecenoic), linoleic acid (Δ^(9c),Δ^(12c) octadecadienoic), linolenic acid (Δ^(9c),Δ^(12c),Δ^(15c)octadecatrienoic), their C₁-C₆ alkylic ester or their mono-, di- ortriglyceride form, or a combination thereof.

By way of examples of sources from plant origins, one may mention, amongothers, rapeseed, sunflower, peanut, olive, hazelnut, corn, soy,flaxseed, linseed, hemp, grapeseed, coconut, palm, cotton grain, bamboo,jojoba, sesame, castor oil, cilantro, safflower oil, tung oil. It isalso possible to start with the esters corresponding to said acids, inparticular methyl, ethyl or propyl esters, and one may also morespecifically cite products of alcoholysis, more specifically ofmethanolysis, in particular of oils.

According to a particular embodiment, the aldehyde of formula (III) isselected from the group comprising formaldehyde, acetaldehyde, propanal,butyraldehyde, valeraldehyde, hexanal, heptanaldehyde, octanal,nonanaldehyde, decanal, undecanaldehyde, laurinaldehyde,tridecanaldehyde, isobutyraldehyde, lisovaleraldehyde,2-methylbutyraldehyde, pivalaldehyde, 2-ethylbutaraldehyde,2-ethylhexanaldehyde, isodecanaldehyde, acroleeine, crotonaldehyde,trans-2-hexen-1-al, trans,trans-2,4-hexadien-1-al, cis-4-heptenal,trans-2-nonen-1-al, cis-4-decenal, citronellal, hydroxycitronellal,1-cyclohexene-1-carboxaldehyde, 3-cyclohexene-1-carboxaldehyde,benzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde,4-methyl-2-phenyl-2-pentenal, para-tertiarybutyl-alpha-methylhydrocinnamic aldehyde, amyl cinnamic aldehyde, glyoxal, glutaraldehyde,furfuraldehyde, 3-(methylthio)propionaldehyde, 2-ethylacroleine,3-methylcrotonaldehyde, 2-methyl-2-butenal, methyl 4-oxobutanoate,cinnamaldehyde, 3-dimethylaminoacroleine, cyclopentanecarboxaldehyde,2,3,4,5,6-pentafluorobenzaldehyde, 4-bromo-2,6-difluorobenzaldehyde,3,5-dibromobenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde,2,6-dinitrobenzaldehyde, 4-chlorobenzaldehyde,2-chloro-4-hydroxybenzaldehyde, 4-fluorobenzaldehyde,5-fluorosalicylaldehyde, 4-nitrobenzaldehyde,4-hydroxy-3-nitrobenzaldehyde, 3,5-dihydroxybenzaldehyde,2,4,6-trihydroxybenzaldehyde, 2-aminobenzaldehyde, 2,4-heptadienal,2,2-dimethyl-4-pentenal, 2-cyanobenzaldehyde, isophtalaldehyde,terephthalaldehyde, 4-formylbenzoic acid, 5-formylsalicylic acid,o,m,p-tolualdehyde, phenylacetaldehyde,2,4-dihydroxy-6-methylbenzaldehyde, 3-vinylbenzaldehyde,hydrocinnamaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, mesitaldehyde,2,4,6-trimethoxybenzaldehyde, 1-naphtaldehyde,biphenyl-4-carboxaldehyde, 3-phenoxybenzaldehyde,4-(4-formylphenoxy)benzaldehyde, diphenylacetaldehyde,9-anthracenecarboxaldehyde, 9-phenanthrenecarboxaldehyde,5-(hydroxymethyl)furfural (HMF), and tris(4-formylphenyl)amine. Forexample, the aldehyde of formula (III) is selected from the groupcomprising acetaldehyde, propanal, butyraldehyde, valeraldehyde,hexanal, heptanaldehyde, octanal, nonanaldehyde, decanal,undecanaldehyde, laurinaldehyde, tridecanaldehyde, isobutyraldehyde,isovaleraldehyde, 2-methylbutyraldehyde, pivalaldehyde,2-ethylbutaraldehyde, 2-ethylhexanaldehyde, isodecanaldehyde, acroleine,crotonaldehyde, trans-2-hexen-1-al, trans,trans-2,4-hexadien-1-al,cis-4-heptenal, trans-2-nonen-1-al, cis-4-decenal, citronellal,hydroxycitronellal, 1-cyclohexene-1-carboxaldehyde,3-cyclohexene-1-carboxaldehyde, benzaldehyde, 3-hydroxybenzaldehyde,4-hydroxybenzaldehyde, 4-methyl-2-phenyl-2-pentenal, glutaraldehyde,furfuraldehyde, 2-ethylacroleine, 3-methylcrotonaldehyde,2-methyl-2-butenal, cinnamaldehyde, 2,3,4,5,6-pentafluorobenzaldehyde,4-bromo-2,6-difluorobenzaldehyde, 3,5-dibromobenzaldehyde,3,5-dibromo-4-hydroxybenzaldehyde, 2,6-dinitrobenzaldehyde,4-chlorobenzaldehyde, 2-chloro-4-hydroxybenzaldehyde,4-fluorobenzaldehyde, 5-fluorosalicylaldehyde, 4-nitrobenzaldehyde,4-hydroxy-3-nitrobenzaldehyde, 3,5-dihydroxybenzaldehyde,2,4,6-trihydroxybenzaldehyde, 2-aminobenzaldehyde,1-cyclohexene-1-carboxaldehyde, 2-cyanobenzaldehyde,4-formylbenzonitrile, terephthalaldehyde, 4-formylbenzoic acid,2,4-dihydroxy-6-methylbenzaldehyde, 3-vinylbenzaldehyde,1-naphtaldehyde, and 5-(hydroxymethyl)furfural (HMF). According to apreferred embodiment, the aldehyde of formula (III) is selected from thegroup comprising hexanal, decanal, citronellal, hydroxycitronellal,3-cyclohexene-1-carboxaldehyde, benzaldehyde, 3-hydroxybenzaldehyde,4-hydroxybenzaldehyde, furfuraldehyde, cinnamaldehyde,3,5-dibromo-4-hydroxybenzaldehyde,4-chlorobenzaldehyde2-chloro-4-hydroxybenzaldehyde,4-fluorobenzaldehyde, 5-fluorosalicylaldehyde, 4-nitrobenzaldehyde,4-hydroxy-3-nitrobenzaldehyde, 3,5-dihydroxybenzaldehyde,2,4,6-trihydroxybenzaldehyde, 2-aminobenzaldehyde,1-cyclohexene-1-carboxaldehyde, terephthalaldehyde, 4-formylbenzoicacid, 3-vinylbenzaldehyde, 1-naphtaldehyde, and5-(hydroxymethyl)furfural (HMF). For example, the aldehyde of formula(III) is selected from the group comprising hexanal, decanal,citronellal, hydroxycitronellal, 3-cyclohexene-1-carboxaldehyde,benzaldehyde, 4-hydroxybenzaldehyde, cinnamaldehyde,4-chlorobenzaldehyde, terephthalaldehyde, 4-formylbenzoic acid, and5-(hydroxymethyl)furfural (HMF). For example, the aldehyde of formula(III) is selected from the group comprising hexanal, decanal,citronellal, hydroxycitronellal, 3-cyclohexene-1-carboxaldehyde,terephthalaldehyde, and benzaldehyde.

According to a particular embodiment, the compound of formula (III) isan aldehyde having the formula R⁵⁰—(CR¹²R¹¹)_(n)—CHO, in which eachidentical or different R¹² is selected from H or C₁-C₆ alkyl, eachidentical or different R¹¹ is selected from H, a halogen atom, —CHO,—OH, or C₁-C₆ alkyl, C₆-C₁₂ aryl, C₆-C₁₂ arylC₁₋₆alkyl, C₁₋₆alkylC₆-C₁₂aryl, n is a whole number comprised between 1 and 20, and R⁵⁰has the same meaning as stated above. According to a particularembodiment, n is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, or 20. According to a particular embodiment,R¹², identical or different, is selected from H or C₁-C₄ alkyl; eachidentical or different R¹¹ is selected from H or C₁-C₄ alkyl, C₆-C₁₂aryl, C₁₋₄ alkylC₆-C₁₂aryl. According to a particular embodiment, R⁵⁰ isselected from the group comprising Cl, F, I, Br, —OH, —SH, cyano, nitro,isocyanate, C₁-C₄ alkoxy, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, —CO₂R⁸, epoxy,or —NR⁹ ₂. For example, R⁵⁰ is selected from the group comprising Cl, F,I, Br, —OH, —SH, cyano, or nitro, preferably —OH, —SH, cyano or nitro,preferably —OH, —SH or cyano.

According to a particular embodiment, the aldehyde of formula (III) isused in an equimolar quantity, less than or more than the compound offormula (II).

According to a particular embodiment, the compound of formula (Ia) or(Ib) is prepared in situ (monotope synthesis process more commonly knownby its English name of a “one-pot” reaction).

According to a particular embodiment, the reaction involves twosuccessive steps comprising: epoxidation of the compound of formula (II)in the presence of molecular or atmospheric oxygen, and at least onealdehyde of formula (III) and optionally in the presence of at least onecatalyst; and the opening of the epoxide (oxirane cycle) optionally inthe presence of at least one catalyst, which catalyst may be the same asor different from that in the epoxidation step. The process allows thesynthesis of multifunctional compounds in a single step throughsuccessive epoxidation and acylation reactions on unsaturated molecules.

One of the innovations of the invention resides in the use of analdehyde that considerably increases the efficacy of the first step ofthe reaction and that, then, is used as an agent to open the oxiranecycle, since the aldehyde is transformed into an acid during the firststep, as illustrated in Diagram 1. One of the innovations of theinvention resides as well in the fact that the epoxide and the acid areonly reaction intermediaries. They are generated in situ during thereaction. Another innovation is in the fact that during epoxidation, theopening reaction has already taken place.

So, the opening agent is generated in situ by the transformation ofaldehyde first into peracid, since it can either regenerate the catalystor react with the unsaturation of the compound (II) to be transformedinto an acid. During the second step, the opening of the epoxide, theacid function allows the opening and the grafting of the molecule ontothe molecule of the epoxidated formula (II), by the creation of an esterlink and a vicinal alcohol function, since the function at the end ofthe ester chain represents a new reaction center (R⁵). According to aparticular embodiment, the vicinal hydroxyl can also react, thusproducing a compound of formula (Ia) and/or (Ib) in which R⁶ is—CO-L¹-R⁵.

According to a particular embodiment, the epoxidation step is carriedout at a temperature of between 0 and 200° C., preferably between 20 and150° C., preferably between 40 and 100° C., preferably between 50 and80° C.

According to a particular embodiment, the epoxide opening step iscarried out at a temperature of between 0 and 300° C., preferablybetween 30 and 300° C., preferably between 30 and 250° C., preferablybetween 30 and 200° C., preferably between 30 and 170° C.

According to a particular embodiment, in the case of a “one pot”reaction, the epoxidation step and the epoxide opening step are carriedout at the same temperature.

Preferably, the opening step is carried out in the presence of nitrogen.The presence of nitrogen allows secondary reactions to be minimized,such as lipidic oxidation in the case of the use of triglycerides ortheir derivatives (autoxidation, photo-oxidation).

According to a particular embodiment, the present process is carried outin the absence of a solvent. Advantageously, the process involves a onepot reaction of compounds of formula (II), using molecular oratmospheric oxygen as the oxidation agent in the presence of a solidcatalyst, an aldehyde and in the absence of a solvent. Advantageously,the process involves a one pot reaction of unsaturated fatty bodies,using molecular or atmospheric oxygen as the oxidation agent in thepresence of a solid catalyst, an aldehyde and in the absence of anysolvent.

According to a particular embodiment, the solid catalyst is immobilizedin a reactor, the compound of formula (II) and the aldehyde of formula(III) are sent into the reactor then the air or molecular oxygen isintroduced, either by bubbling at atmospheric pressure, or underpressure. According to a particular embodiment, the environment isbrought to the reaction temperature, preferably between 0 and 200° C.,preferably between 20 and 150° C., preferably between 40 and 100° C.,preferably between 50 and 80° C.

Samples may be taken regularly in order to gauge the progress of theepoxidation reaction. When it is complete, the air may be replaced by aninert gas, typically nitrogen, and the environment may be brought to ahigher temperature, preferably between 30 and 200° C. in order to causethe epoxide opening reaction by the acid generated in situ. The catalystmay optionally be added in this step to catalyze the opening reaction.This catalyst may be solid, such as a zeolite, a hydrotalcite, anactivated carbon a functionalized silica or a polymeric resin such asbasic and/or acidic polymer resins such as those sold under the nameAmberlyst® or Amberlite® or a combination thereof. This catalyst may behomogenous such as a mineral base (KOH, NaOH), a primary, secondary ortertiary amine (hexylamine, dihexylamine, trihexylamine) or acombination thereof.

Once the reaction is completed, the environment may be brought back toambient temperature and taken from the reactor, which may again receivereagents without any specific treatment, since the catalyst may bereused without reactivation.

According to a particular embodiment, for example for industrial use,the process is carried out continuously or in two or several separatereactors.

The present invention relates also to the use of a process as describedabove for the preparation of polyhydroxylated polyesters.

The present invention also relates to compounds of formula (Ia), (Ib),(Ic) or (Id) that can be obtained through the process according to theinvention, and their use, for example, in the preparation of polymers orbiopolymers, in particular polyurethanes, of polyhydroxylatedpolyesters, bioplastics, surfactants, plasticizers or lubricants.According to a preferred embodiment, the invention also relates to thecompounds of formula (Ia), (Ib), (Ic) or (Id) directly obtained via theprocess according to the invention, and their use, for example, in thepreparation of polymers or biopolymers, in particular of polyurethanes,of polyhydroxylated polyesters, or bioplastics, of surfactants,plasticizers or lubricants. Preferably, the invention relates to the useof a compound of formula (Ia) or (Ib) directly obtained according to theprocess according to the invention, as a monomer for the preparation ofpolyurethane.

The invention also relates to a compound of formula (Ie) or (If), astereoisomer thereof, or a mixture thereof,

wherein:

R¹⁶ is H or is selected from the group comprising —CO—(CR²¹R²²)_(q)—R²³,—CO—, C₆-C₁₂ aryl, and —CO—C₅-C₁₂ cycloalkenyl, with each group beingoptionally substituted by one or several groups, either identical ordifferent, selected from the group comprising a halogen atom, —OH,—OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl; preferably R¹⁶ is H or is selectedfrom the group comprising —CO—(CR²¹R²²)_(q)—R²³, —CO—C₆-C₁₀ aryl, and—CO—C₅-C₁₀ cycloalkenyl, with each group being optionally substituted byone or several groups, either identical or different, selected from thegroup comprising a halogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;preferably R¹⁶ is H or is selected from the group comprising—CO—(CR²¹R²²)_(q)R²³, —CO—C₆ aryl, and C₅-C₈ cycloalkenyl, with eachgroup being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₄ alkyl;

R¹⁷ is selected from the group comprising a C₂-C₂₀ alkyl and a C₂-C₂₀alkenyl, with each group being optionally substituted by one or severalidentical or different groups, selected from a C₁-C₆ alkyl, a C₆ aryl,—OR¹⁶, or —CO₂R²⁴; preferably R¹⁷ is selected from the group comprisinga C₂-C₁₂ and a C₂-C₂₀ alkenyl, with each group being optionallysubstituted by 1, 2, 3 or 4 groups, either identical or different,selected from a C₁-C₆ alkyl, a C₆ aryl, —OR¹⁶, or —CO₂R²⁴; preferablyR¹⁷ is selected from the group comprising a C₂-C₁₂ alkyl and a C₂-C₂₀alkenyl, with each group being optionally substituted by 1, 2, 3 or 4groups, either identical or different, selected from a C₁-C₆ alkyl,—OR¹⁶, or —CO₂R²⁴; R¹⁷ is preferably a C₂-C₁₀ alkyl optionallysubstituted by 1, 2, or 3 groups, that is a C₂-C₁₀ alkyl, optionallysubstituted by 1, 2, or 3 identical or different groups, selected from aC₁-C₄ alkyl, or —CO₂R²⁴;

R¹⁸ is H or is selected from the group comprising a C₂-C₂₀ alkyl and aC₂-C₂₀ alkenyl, with each group being optionally substituted by one orseveral identical or different groups, selected from a C₁-C₆ alkyl, a C₆aryl, —OR¹⁶, or —CO₂R²⁴; preferably R¹⁸ is H or is selected from thegroup comprising a C₂-C₁₂ and a C₂-C₂₀ alkenyl, with each group beingoptionally substituted by 1, 2, 3 or 4 groups, either identical ordifferent, selected from a C₁-C₆ alkyl, a C₆ aryl, —OR¹⁶, or —CO₂R²⁴;preferably R¹⁸ is H or is selected from the group comprising a C₂-C₁₂and a C₂-C₂₀ alkenyl, with each group being optionally substituted by 1,2, 3 or 4 groups, either identical or different, selected from a C₁-C₆alkyl, —OR¹⁶, or —CO₂R²⁴; preferably R¹⁸ is H or a C₂-C₁₀ alkyloptionally substituted by 1, 2, or 3 identical or different groups,selected from a C₁-C₄ alkyl or —CO₂R²⁴; or R¹⁷ and R¹⁸ may, with thecarbons to which they are bound, form a group selected from a C₅-C₁₂cycloalkyl or C₅-C₁₂ cycloalkenyl, with each group being optionallysubstituted by one or several groups, either identical or different,selected from the group comprising a halogen atom, —OR¹⁶, —OCOR¹⁹,—CO₂R²⁴, and C₁-C₆ alkyl; preferably R¹⁷ and R¹⁸ may, with the carbonsto which they are bound, form a group selected from a C₅-C₁₀ cycloalkylor a C₅-C₁₀ cycloalkenyl, with each group being optionally substitutedby 1, 2, 3, or 4 groups, either identical or different, selected fromthe group comprising a halogen atom, —OR¹⁶, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆alkyl; preferably R¹⁷ and R¹⁸ may, with the carbons to which they arebound, form a group selected from a C₅-C₈ cycloalkyl or C₅-C₈cycloalkenyl, with each group being optionally substituted by 1, 2 or 3groups, either identical or different, selected from the groupcomprising —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₄ alkyl;

R¹⁹ is selected from the group comprising-(CR²¹R²²)_(q)—R²³, a C₆-C₁₂aryl, and a C₅-C₁₂ cycloalkenyl, with each group being optionallysubstituted by one or several groups, either identical or different,selected from the group comprising a halogen atom, —OH, —OCOR¹⁹,—CO₂R²⁴, and C₁-C₆ alkyl; preferably R¹⁹ is selected from the groupcomprising —(CR²¹R²²)_(q)—R²³, a C₆-C₁₀ aryl, and a C₅-C₁₀,cycloalkenyl, with each group being optionally substituted by 1, 2, 3 or4 groups, that are identical or different, selected from the groupcomprising a halogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;preferably R¹⁹ is selected from the group comprising —(CR²¹R²²)_(q)—R²³,a C₆ aryl, and a C₅-C₈ cycloalkenyl, with each group being optionallysubstituted by 1, 2, 3, or 4 groups, either identical or different,selected from the group comprising a halogen atom, —OH, —OCOR19,—CO₂R24, and C₁-C₄ alkyl;

q is a whole number comprises between 3 and 12; preferably q is a wholenumber comprised between 4 and 12, for example q may be 4, 5, 6, 7, 8,9, 10, 11 or 12;

each identical or different R²¹ is selected from H or a C₁-C₆ alkyl;preferably each identical or different R²¹ is selected from H or a C₁-C₄alkyl;

each identical or different R²² is selected from H or a C₁-C₆ alkyl;preferably each identical or different R²² is selected from H or a C₁-C₄alkyl;

R²³ is H or —OH, or is selected from the group comprising a C₁-C₆ alkyland a C₆-C₁₂ aryl, with each group being optionally substituted by oneor several groups, either identical or different, selected from thegroup comprising a halogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;preferably R²³ is selected from H, —OH or a C₁-C₄ alkyl optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising a halogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, andC₁-C₆ alkyl;

R²⁴ is H or a C₁-C₆ alkyl optionally substituted by one or severalgroups, either identical or different, selected from the groupcomprising —OH, —O—COR²⁵, and C₁-C₆ alkyl; preferably R²⁴ is H or aC₁-C₄ alkyl, optionally substituted by 1, 2, or 3 identical or differentgroups, selected from —OH, —O—COR²⁵, or C₁-C₄; alkyl; preferably R²⁴ isH or a C₁-C₄ alkyl optionally substituted by 1, 2, or 3 identical ordifferent groups, selected from —OH, —O—COR²⁵, or C₁-C₄ alkyl;

R²⁵ is selected from the group comprising C₂-C₂₀ alkyl; and C₂-C₂₀alkenyl, with each group being optionally substituted by one or severalgroups, either identical or different, selected from the groupcomprising —OH, epoxy, —OR¹⁶, and —OCOR¹⁹; preferably R²⁵ is selectedfrom the group comprising C₂-C₂₀ alkyl and C₂-C₂₀ alkenyl, with eachgroup being optionally substituted by 1, 2 or 3 groups, either identicalor different, selected from the group comprising —OH, epoxy, —OR¹⁶, and—OCOR¹⁹.

The invention also relates to a compound having formula (Ie) or (If), astereoisomer thereof, a mixture thereof, an oligomer and/or a polymerthereof.

According to a preferred embodiment, the invention relates to a compoundhaving formula (Ie) or (If), an oligomer and/or a polymer thereof,wherein R¹⁶ is H or is selected from the group comprising—CO—(CR²¹R²²)_(q)—R²³, —CO—C₆-C₁₂ aryl, and —CO—C₅-C₁₂ cycloalkenyl,with each group being optionally substituted by one or several groups,either identical or different, selected from the group comprising ahalogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;

R¹⁷ is a C₃-C₂₀ alkyl optionally substituted by one or several identicalor different groups, selected from a C₁-C₆ alkyl, —OR¹⁶, or —CO₂R²⁴;preferably R¹⁷ is a C₃-C₁₂ alkyl, optionally substituted by one orseveral identical or different groups, selected from a C₁-C₆ alkyl,—OR¹⁶, or —CO₂R²⁴;

R¹⁸ is H or a C₃-C₂₀ alkyl optionally substituted by one or severalidentical or different groups, selected from a C₁-C₆ alkyl —OR¹⁶, or—CO₂R²⁴; preferably R¹⁸ is H or a C₃-C₁₂ alkyl optionally substituted byone or several identical or different groups, selected from a C₁-C₆alkyl, —OR¹⁶, or —CO₂R²⁴; or R¹⁷ and R¹⁸ may, with the carbons to whichthey are bound, form a group selected from a C₅-C₁₂ cycloalkyl or aC₅-C₁₂ cycloalkenyl with each group being optionally substituted by oneor several groups, either identical or different, selected from thegroup comprising a halogen atom, —OR¹⁶, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆alkyl; or R¹⁷ and R¹⁸ may preferably, with the carbons to which they arebound, form a group selected from a C₅-C₁₂ cycloalkyl or a C₅-C₁₂cycloalkenyl, with each group being optionally substituted by 1, 2, 3 or4 identical or different groups, selected from —OH, —OCOR¹⁹, —CO₂R²⁴, orC₁-C₆ alkyl;

R¹⁹ is selected from the group comprising —(CR²¹R²²)_(q)—R²³, a C₆-C₁₂aryl, and a C₅-C₁₂ cycloalkenyl, with each group being optionallysubstituted by one or several groups, either identical or different,selected from the group comprising a halogen atom, —OH, —OCOR¹⁹,—CO₂R²⁴, and C₁-C₆ alkyl; preferably R¹⁹ is selected from the groupcomprising —(CR²¹R²²)_(q)—R²³, a C₆ aryl, and a C₅-C₁₂ cycloalkenyl,with each group being optionally substituted by one or several groups,either identical or different, selected from the group comprising —OH,—OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;

q is a whole number comprised between 3 and 12; for example q is 3, 4,5, 6, 7, 8, 9, 10 or 11;

each identical or different R²¹ is selected from H or a C₁-C₆ alkyl;

each identical or different R²² is selected from H or a C₁-C₆ alkyl;

R²³ is H or —OH, or is selected from the group comprising a C₁-C₆ alkyland a C₆-C₁₂ aryl, with each group being optionally substituted by oneor several groups, either identical or different, selected from thegroup comprising a halogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;

R²⁴ is H or a C₁-C₆ alkyl optionally substituted by one or severalidentical or different groups, selected from —OH, —O—COR²⁵, or C₁-C₆alkyl; and

R²⁵ is selected from the group comprising C₂-C₂₀ alkyl, and C₂-C₂₀alkenyl, with each group being optionally substituted by one or severalgroups, either identical or different, selected from the groupcomprising —OH, epoxy, —OR¹⁶, and —OCOR¹⁹;

provided that the compound is not methyl9-(hexanoyloxy)-10-hydroxyoctadecanoate, methyl10-(hexanoyloxy)-9-hydroxyoctadecanoate, the octanoic ester of methylhydroxy-oleate, the 2-ethyl-hexyl ester of methyl hydroxyoleate, methylhydroxybenzoyloxy-octadodecaneate, 1,2-heptanediol dicaproate and1,2-octanediol dicaproate.

According to a preferred embodiment, the invention relates to a compoundof formula (Ie) or (If), wherein: R¹⁶ is H; and

R¹⁷ is selected from the group comprising a C₂-C₂₀ alkyl and a C₂-C₂₀alkenyl, with each group being optionally substituted by one or severalidentical or different groups, selected from a C₁-C₆ alkyl, a C₆ aryl,or —OR¹⁶, preferably R¹⁷ is selected from the group comprising a C₂-C₁₂and a C₂-C₂₀ alkenyl, with each group being optionally substituted by 1,2, 3 or 4 groups, either identical or different, selected from a C₁-C₆alkyl, or a C₆ aryl, —OR¹⁶; preferably R¹⁷ is selected from the groupcomprising a C₂-C₁₂ and a C₂-C₂₀ alkenyl, with each group beingoptionally substituted by 1, 2, 3 or 4 groups, either identical ordifferent, selected from a C₁-C₆ alkyl, or —OR¹⁶; preferably R¹⁷ is aC₂-C₁₀ alkyl, optionally substituted by 1, 2, or 3 identical ordifferent groups, selected from a C₁-C₄ alkyl;

R¹⁸ is H or is selected from the group comprising a C₂-C₂₀ alkyl and aC₂-C₂₀ alkenyl, with each group being optionally substituted by one orseveral identical or different groups, selected from a C₁-C₆ alkyl, aC₆, aryl or —OR¹⁶; preferably R¹⁸ is H or is selected from the groupcomprising a C₂-C₁₂ and a C₂-C₂₀ alkenyl, with each group beingoptionally substituted by 1, 2, 3 or 4 groups, either identical ordifferent, selected from a C₁-C₆ alkyl, a C₆ aryl, or —OR¹⁶, preferablyR¹⁸ is H or is selected from the group comprising a C₂-C₁₂ and a C₂-C₂₀alkenyl, with each group being optionally substituted by 1, 2, 3 or 4groups, either identical or different, selected from a C₁-C₆ alkyl, or—OR¹⁶; preferably R¹⁸ is H or a C₂-C₁₀ alkyl, optionally substituted by1, 2, or 3 identical or different groups, selected from a C₁-C₄ alkyl;or R¹⁶ is H or is selected from the group comprising—CO—(CR²¹R²²)_(q)—R²³, —CO—C₆-C₁₂ aryl, and —CO—C₅-C₁₂ cycloalkenyl,with each group being optionally substituted by one or several groups,either identical or different, selected from the group comprising ahalogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl; and R¹⁷ and R¹⁸form with the carbons to which they are bound a group selected from aC₅-C₁₂ cycloalkyl or a C₅-C₁₂ cycloalkenyl, with each group beingoptionally substituted by one or several groups, either identical ordifferent, selected from the group comprising a halogen atom, —OR¹⁶,—OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl; or R¹⁷ and R¹⁸ may preferably, withthe carbons to which they are bound, form a group selected from a C₅-C₁₀cycloalkyl or a C₅-C₁₀ cycloalkenyl, with each group being optionallysubstituted by 1, 2, 3, or 4 groups, either identical or different,selected from the group comprising a halogen atom, —OR¹⁶—OCOR¹⁹,—CO₂R²⁴, and C₁-C₆ alkyl; or R¹⁷ and R¹⁸ may preferably, with thecarbons to which they are bound, form a group selected from a C₅-C₈cycloalkyl or a C₅-C₈ cycloalkenyl, with each group being optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₄ alkyl;

R¹⁹ is selected from the group comprising —(CR²¹R²²)_(q)—R²³, a C₆-C₁₂aryl, and a C₅-C₁₂ cycloalkenyl, with each group being optionallysubstituted by one or several groups, either identical or different,selected from the group comprising a halogen atom, —OH, —OCOR¹⁹,—CO₂R²⁴, and C₁-C₆ alkyl; preferably R¹⁹ is selected from the groupcomprising —(CR²¹R²²)_(q)—R²³, a C₆-C₁₀ aryl, and a C₅-C₁₀ cycloalkenyl,with each group being optionally substituted by 1, 2, 3, or 4 identicalor different groups, selected from the group comprising a halogen atom,—OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl; preferably R¹⁹ is selected fromthe group comprising —(CR²¹R²²)_(q)—R²³, a C₆ aryl, and a C₅-C₈cycloalkenyl, with each group being optionally substituted by 1, 2, or 3identical or different groups, selected from the group comprising ahalogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₄ alkyl;

q is a whole number comprised between 3 and 12; preferably q is a wholenumber comprised between 4 and 12, for example q may be 4, 5, 6, 7, 8,9, 10, 11 or 12;

each identical or different R²¹ is selected from H or a C₁-C₆ alkyl;preferably each identical or different R²¹ is selected from H or a C₁-C₄alkyl;

each identical or different R²² is selected from H or a C₁-C₆ alkyl;preferably each identical or different R²² is selected from H or a C₁-C₄alkyl;

R²³ is H or —OH, or is selected from the group comprising a C₁-C₆ alkyland a C₆-C₁₂ aryl, with each group being optionally substituted by oneor several groups, either identical or different, selected from thegroup comprising a halogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;preferably R²³ is selected from H, —OH or a C₁-C₄ alkyl optionallysubstituted by 1, 2 or 3 groups, either identical or different, selectedfrom the group comprising a halogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, andC₁-C₆ alkyl;

R²⁴ is H or a C₁-C₆ alkyl optionally substituted by one or severalgroups, either identical or different, selected from the groupcomprising —OH, —O—COR²⁵, and C₁-C₆ alkyl; preferably R²⁴ is H or aC₁-C₄ alkyl, optionally substituted by 1, 2, or 3 identical or differentgroups, selected from —OH, —O—COR²⁵, or C₁-C₄ alkyl; preferably R²⁴ is Hor a C₁-C₄ alkyl optionally substituted by 1, 2, or 3 identical ordifferent groups, selected from —OH, —O—COR²⁵, or C₁-C₄ alkyl;

R²⁵ is selected from the group comprising C₂-C₂₀ alkyl; and C₂-C₂₀alkenyl, with each group being optionally substituted by one or severalgroups, either identical or different, selected from the groupcomprising —OH, epoxy, —OR¹⁶, and —OCOR¹⁹; preferably R²⁵ is selectedfrom the group comprising C₂-C₂₀ alkyl, and C₂-C₂₀ alkenyl, with eachgroup being optionally substituted by 1, 2 or 3 groups, either identicalor different, selected from the group comprising —OH, epoxy, —OR¹⁶, and—OCOR¹⁹.

According to a preferred embodiment, the invention relates to a compoundhaving formula (Ie) or (If), wherein:

R¹⁶ is H or is selected from the group comprising —CO—(CR²¹R²²)_(q)—R²³,—CO—C₆-C₁₂ aryl, and —CO—C₅-C₁₂ cycloalkenyl, with each group beingoptionally substituted by one or several groups, either identical ordifferent, selected from the group comprising a halogen atom, —OH,—OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;

R¹⁷ is a C₃-C₂₀ alkyl optionally substituted by one or several identicalor different groups, selected from a C₁-C₆ alkyl, —OR¹⁶, or —CO₂R²⁴;preferably R¹⁷ is a C₃-C₁₂ alkyl, optionally substituted by one orseveral identical or different groups, selected from a C₁-C₆ alkyl,—OR¹⁶, or —CO₂R²⁴;

R¹⁸ is H or a C₃-C₂₀ alkyl optionally substituted by one or severalidentical or different groups, selected from a C₁-C₆ alkyl, —OR¹⁶, or—CO₂R²⁴; preferably R¹⁸ is H or a C₃-C₁₂ alkyl optionally substituted byone or several identical or different groups, selected from a C₁-C₆alkyl, —OR¹⁶, or —CO₂R²⁴;

or R¹⁷ and R¹⁸ may, with the carbons to which they are bound, form agroup selected from a C₅-C₁₂ cycloalkyl or a C₅-C₁₂ cycloalkenyl, witheach group being optionally substituted by one or several groups, eitheridentical or different, selected from the group comprising a halogenatom, —OR¹⁶, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl; or R¹⁷ and R¹⁸ maypreferably, with the carbons to which they are bound, form a groupselected from a C₅-C₁₂ cycloalkyl or a C₅-C₁₂ cycloalkenyl, with eachgroup being optionally substituted by 1, 2, 3 or 4 groups, eitheridentical or different, selected from —OH, —OCOR¹⁹, —CO₂R²⁴, or C₁-C₆alkyl;

R¹⁹ is selected from the group comprising —(CR²¹R²²)_(q)—R²³, a C₆-C₁₂aryl, and a C₅-C₁₂ cycloalkenyl, with each group being optionallysubstituted by one or several groups, either identical or different,selected from the group comprising a halogen atom, —OH, —OCOR¹⁹,—CO₂R²⁴, and C₁-C₆ alkyl; preferably R¹⁹ is selected from the groupcomprising —(CR²¹R²²)_(q)—R²³, a C₆ aryl, and a C₅-C₁₂ cycloalkenyl,with each group being optionally substituted by one or several groups,either identical or different, selected from the group comprising —OH,—OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;

q is a whole number comprised between 3 and 12; for example q is 3, 4,5, 6, 7, 8, 9, 10 or 11;

each identical or different R²¹ is selected from H or a C₁-C₆ alkyl;

each identical or different R²² is selected from H or a C₁-C₆ alkyl;

R²³ is H or —OH, or is selected from the group comprising a C₁-C₆ alkyland a C₆-C₁₂ aryl, with each group being optionally substituted by oneor several groups, either identical or different, selected from thegroup comprising a halogen atom, —OH, —OCOR¹⁹, —CO₂R²⁴, and C₁-C₆ alkyl;

R²⁴ is H or a C₁-C₆ alkyl optionally substituted by one or severalgroups, either identical or different, selected from —OH, —O—COR²⁵, orC₁-C₆ alkyl; and

R²⁵ is selected from the group comprising C₂-C₂₀ alkyl, and C₂-C₂₀alkenyl, with each group being optionally substituted by one or severalgroups, either identical or different, selected from the groupcomprising —OH, epoxy, —OR¹⁶, and —OCOR¹⁹.

The present invention also relates to an oligomer and/or a polymer ofcompounds of formula (Ie) or (If), such as the compounds of formula (Ig)or (Ih),

in which R¹⁶, R¹⁷, R¹⁸, R¹⁹, are as described above and p is a wholenumber comprised between 1 and 10,000, preferably p is a whole numbercomprised between 1 and 1,000, for example p is a whole number comprisedbetween 1 and 100.

According to a particular embodiment, the present invention relates to acompound of formula (Ie) or (If) selected from the group comprising9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate,10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate,methyl 9-(decanoyloxy)-10-hydroxyoctadecanoate; methyl10-(decanoyloxy)-9-hydroxyoctadecanoate, 2-hydroxyoctyl hexanoate,1-hydroxyoctan-2-yl hexanoate; 5-hydroxyoctan-4-yl hexanoate;octane-4,5-diyl dihexanoate; 2-hydroxycyclooctyl hexanoate;cyclooctane-1,2-diyl dihexanoate; 4-formyl-2-hydroxycyclohexylcyclohex-3-enecarboxylate; 5-formyl-2-hydroxycyclohexyl;7-oxa-bicyclo[4.1.0]heptane-3-carboxylate;4-(cyclohex-3-enecarbonyloxy)-3-hydroxycyclohexanecarboxylic acid; and3-(7-oxa-bicyclo[4.1.0]heptane-3-carbonyloxy)-4-hydroxycyclohexanecarboxylicacid.

According to a particular embodiment, the present invention relates to acompound of formula (Ia), or (Ib), that may be obtained through thepresent process, having formula (Ie) or (If).

According to a particular embodiment, the compounds of formula (Ia),(Ib), (Ic), (Id), (Ie), (If), (Ig) or (Ih) may be used for thepreparation of polymers, biopolymers, surfactants, plasticizers orlubricants, or for the preparation of polyurethane.

According to a preferred embodiment, the present invention concerns theuse of a compound of formula (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig) or(Ih), or of methyl 9-(hexanoyloxy)-10-hydroxyoctadecanoate, methyl10-(hexanoyloxy)-9-hydroxyoctadecanoate, the octanoic ester of methylhydroxy-oleate, the 2-ethyl-hexyl ester of methyl hydroxyoleate, methylhydroxybenzoyloxy-octadodecaneate, 1,2-heptanediol dicaproate and1,2-octanediol dicaproate; as a monomer for the preparation ofpolyurethane.

Polyurethane is understood to mean polymers resulting primarily from thereaction of compounds of formula (Ia), (Ib), (Ic), (Id), (Ie), (If),(Ig) or (Ih) or a combination thereof with isocyanates. Polyurethane isalso understood to mean polymers resulting from the reaction ofcompounds of formula (Ia), (Ib), (Ie), (Id), (Ie), (If), (Ig) or (Ih) ora combination thereof with isocyanates that contain, aside from urethanefunctions, other types of functions, in particular triisocyanate cyclesformed by the trimerization of isocyanates.

The invention also relates to a formulation comprising:

-   -   at least one compound of formula (Ia), (Ib), (Ic), (Id), (Ie),        (If), (Ig) or (Ih) or a combination thereof, and    -   at least one isocyanate.

These formulations may be used to prepare polyurethanes, in particularthermoplastic or thermohardened polyurethanes. The formulationsaccording to the invention may also include one or several polyolstraditionally used to prepare polyurethanes. Polyether-polyols andpolyester-polyols may also be cited.

All isocyanates traditionally used to manufacture polyurethanes may beimplemented in the use or formulations according to the invention.Preferably, the isocyanate is a polyisocyanate. The polyisocyanate usedmay be selected from aliphatic, aromatic, cycloaliphatic and thoseisocyanates that contain an isocyanurate cycle in their molecule; havingat least two isocyanate functions in their molecule, likely to reactwith one or several hydroxyl functions of a compound of formula (Ia),(Ib), (Ic), (Id), (Ie), (If), (Ig) or (Ih) to form a three-dimensionalpolyurethane network causing the reticulation of the formulation.

In regards to polyisocyanates well suited in the context of the presentinvention, one can specifically cite: hexamethylenediisocyanate (HMDI,HDI, or 1,6-diisocyanatohexane), diphenylmethanediisocyanate (MDI) inthe form of its 2,4′,2,2′ and 4,4′ isomers or a mixture thereof, toluenediisocyanate (TDI), isophoronediisocyanate (IPDI),dicyclohexylmethanediisocyanate (DCI); naphthalene 1,5-diisocyanate(NDI), p-phenylene diisocyanate (PPDI),3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), or 4,4′-dibenzyldiisocyanate (DBDI), or a mixture thereof.

According to a preferred embodiment, compounds of formula (Ia), (Ib),(Ic), (Id), (Ie), (If), (Ig) or (Ih) originate from the plant world. Theend products that use these polymers are therefore advantageouslypolymers that originate from the plant world. The product of thereaction, preferably a “one pot” reaction, mentioned above, on avegetable oil, is a functionalized molecule, so that it may be used asraw material for the fabrication of plastic material. This molecule isclassified as a synthon (building block). Various types of plastics(bioplastics) may be envisaged depending on the nature of the functionprovided by the synthesis procedure.

The following examples are given for purposes of illustration and arenon-limiting of this invention, and are subject to variants easilyaccessible to a person skilled in the art.

EXAMPLES Example 1

This example presents a comparison of various catalysts consisting of ametal deposited on a silicon media. All catalysts were prepared usingionic exchange starting from a colloidal silica stabilized with ammoniumions and metal chloride corresponding to the active species. These itemswere tested in regards to the functionalization reaction of methyloleate by hydroxycitronellal which lead to the synthesis of9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate andof 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoateas illustrated in Diagram 2.

The reaction was carried out in a 100 ml glass reactor with mechanicalagitation. Twenty-five grams (25.0 g) of methyl ester of sunflower oilHTO (high oleic content—purity: 85% methyl oleate) as well as 13.0 g ofhydroxycitronellal (FCC Grade: Purity≧95%—Sigma-Aldrich, Ref. W258318)were introduced into the reactor. The solid catalyst of the metal typesupported on silica contains 5% by weight of the quantity of methyloleate engaged, i.e. 250 mg. The environment was heated to 80° C. withcontinuous air bubbling. The air flow was controlled by a ball flowmeter at 70 ml/min. After 7 hours of reaction time, the air flow wasstopped and the reaction medium was raised to 150° C. These parameterswere maintained for 5 additional hours. Samples of the reaction mediumwere taken at regular intervals in order to determine the status of thereaction. The reagent conversion rates and the yield rates of thedesired products after 7 and 12 hours of reaction time are shown inTable 1:

TABLE 1 Conversion Function- into alized Conversion hydroxy- Epoxideproducts Type of Reaction into methyl citronellal^(a) yield yieldcatalyst time (hr.) oleate (%) (%) (%) (%) no catalyst 7 37 70 27 11 1246 92 9 24 Ru/SiO₂ 7 75 95 52 24 12 80 100 13 39 Co/SiO₂ 7 76 100 31 1912 77 100 16 29 Zn/SiO₂ 7 66 99 30 20 12 69 100 10 27 Ni/SiO₂ 7 51 90 3415 12 59 98 13 25 Cr/SiO₂ 7 49 89 31 15 12 56 97 13 25 Cu/SiO₂ 7 34 9024 16 12 38 97 11 22 Rh/SiO₂ 7 34 86 18 17 12 40 96 8 26 ^(a)valuescalculated using gas chromatography ^(b)values calculated using stericexclusion chromatography

The composition of the reaction medium was determined by gas phasechromatographic analysis. The Agilent Technologies 6870N chromatographis equipped with a capillary column (SGE-BPX-70-length: 30 m, insidediameter: 0.25 mm, film thickness: 0.25 μm), of a split/splitlessinjector and a flame ionization detector (temperature of the injectorand the detector: 280° C.). The temperature program of the furnace wasas follows: 80° C. (0 min.)-13° C./min.-180° C. (6 min.)-13°C./min.-220° C. (6 min.)-17° C./min.-250° C. (10 min.).

The hold time for the various products under the conditions describedabove are as follows: dodecane (2.9 min.); hydroxycitronellal (8.9min.); methyl oleate (12.6 min.); methyl trans-9,10epoxy-stearate (18.9min.); methyl cis-9,10-epoxy-stearate (19.2 min).

The conversion of reagents at time t is expressed as follows: (number ofinitial moles of reagent−number of moles of reagent at time t)/number ofinitial moles of reagent*100.

The epoxide yield at time t was calculated as follows: number of molesof epoxide at time t/(number of initial moles of methyl oleate*relativeresponse coefficient of 9,10-epoxystearate in relation to methyloleate)*100.

The functionalized products, i.e. the methyl octadecanoate9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy) and the methyloctadecanoate 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy), wereanalyzed by steric exclusion chromatography.

The Waters Alliance 2695 chromatograph is equipped with a refractionindex detector (RI 410) and with two different columns (Styrage®-HR 0.5and Styragel®-HR 1). The temperature of the furnace containing thecolumns is set at 30° C. and tetrahydrofurane (THF) is used as an eluentat a flow rate of 0.8 ml/min.

Under these conditions, the hold times were as follows: products withhigh molecular weight (>1000 uma; 15.1 min); functionalized products(16.2 min.); methyl oleate and methyl 9,10-epoxy-stearate (18.1 min.);hydroxycitronellal (19.0 min.).

The functionalized products yield is the relative surface area of thechromatographic peak expressed as a percentage of the total of allpeaks.

Example 2

This example describes the synthesis of functionalized compoundsstarting from the methyl oleate. Several aldehydic reagents were tested,comprising hexanal, decanal and benzaldehyde. These three tests lead tothe formation of the following products, respectively: methyl9-(hexanoyloxy)-10-hydroxyoctadecanoate and methyl10-(hexanoyloxy)-9-hydroxyoctadecanoate if hexanal is used; methyl9-(decanoyloxy)-10-hydroxyoctadecanoate and methyl10-(decanoyloxy)-9-hydroxyoctadecanoate for decanal; and lastly methyl9-(benzoyloxy)-10-hydroxyoctadecanoate and methyl10-(benzoyloxy)-9-hydroxyoctadecanoate when benzaldehyde was used. Thesethree reactions are presented in Diagrams 3, 4 and 5.

The reaction was carried out in a 100 ml glass reactor with mechanicalagitation. In all cases, a weight of 25.0 g of methyl ester of sunfloweroil HTO (high oleic content—purity: 85% methyl oleate) was placed in thereactor. A quantity of aldehyde was added; the quantity is equivalent toapproximately one and one-half the number of moles of methyl oleateused. So, for the hexanal presence test, a quantity equal to 7.1 g ofhexanal (purity: 98%-Sigma-Aldrich-ref.: 115606) was placed in thereactor. For decanal, this quantity was equivalent to 11.2 g (purity:98% 0 Sigma-Aldrich-ref. D7384) and in the case of benzaldehyde, 8.6 gof benzaldehyde (purity: 99%-Sigma-Aldrich-ref.: B 1334) were added. Thesolid ruthenium on silica catalyst, containing 1.5% by weight ofruthenium, was added to the reaction mix at a ratio of 2% by weight ofthe quantity of methyl oleate used, i.e. 500 mg.

Then, the medium was heated to 80° C. by a continuous bubbling air flowat atmospheric pressure. The air flow rate was controlled by a ball flowmeter and was 30 ml/min. In the case of hexanal and benzaldehyde, after6 hours of reaction, the air flow rate was stopped and the reactionmedium was placed in an inert atmosphere (nitrogen). In the case ofdecanal, the same operation was carried out after 10 hours of reactiontime. In all cases, the time necessary for total conversion of thealdehyde was allotted. Then, the reaction temperature was increased to150° C. These parameters were maintained for 20 additional hours in thecase of hexanal, 15 hours for decanal and 9 hours for benzaldehyde.Samples of the reaction medium were taken at regular intervals in orderto determine the progress of the reactions. The composition of thevarious reaction media after each reaction step is shown in Table 2:

TABLE 2 Function- alized Conversion Conversion products Type of Time tomethyl to aldehyde Epoxide yield aldehyde (hours) oleate (%) (%) yield(%) (%) hexanal 6 63 100 47 0 20 76 100 11 10 decanal 10 92 100 45 2 2595 100 10 7 benz- 6 100 93 56 0 aldehyde 15 100 96 7 17

The composition of the reaction medium was determined by gas phasechromatographic analysis. The Agilent Technologies 6870N chromatographused is as described in Example 1.

Two different temperature programs were used. The first was as follows:50° C. (5 min.)-10° C./min.-100° C. (5 min.)-10° C./min.-150° C. (5min.)-10° C./min.-220° C. (5 min.)-10° C./min.-250° C. (5 min.).

This program allowed hexanal in particular to be detected. The hold timeof the various products under the conditions described above, with apressure level at the head of the column equal to 16.32 psi were asfollows: hexanal (6.9 min.); dodecane (8.1 min.); methyl oleate (30.0min.); methyl trans-9,10-epoxy-stearate (34.5 min); methylcis-9,10-epoxy-stearate (34.9 min).

The conversion of the reagents at time t is expressed as described inExample 1. The epoxide yield at time t was calculated as described inExample 1.

The second temperature program for the furnace was as follows: 80° C. (0min.)-13° C./min.-180° C. (6 min.)-13° C./min.-220° C. (6 min.)-17°C./min.-250° C. (10 min.). The functionalized products were detectedupon completion of the analysis.

The hold time for the various products at the conditions described abovewere as follows: dodecane (2.9 min.); decanal (5.2 min.); benzaldehyde(5.4 min.); methyl oleate (12.6 min.); methyl trans-9,10-epoxy-stearate(18.9 min.); methyl cis-9,10-epoxy-stearate (19.2 min.); methyl9-(hexanoyloxy)-10-hydroxyoctadecanoate and methyl methyl10-(hexanoyloxy)-9-hydroxyoctadecanoate (29.8 et 29.9 min.); methyl9-(decanoyloxy)-10-hydroxyoctadecanoate and methyl10-(decanoyloxy)-9-hydroxyoctadecanoate (34.4 et 34.5 min.); methyl9-(benzoyloxy)-10-hydroxyoctadecanoate and methyl10-(benzoyloxy)-9-hydroxyoctadecanoate (38.7 et 38.9 min.).

Yields of functionalized products were calculated by assigning aresponse factor equal to one to a surface area of the correspondingchromatographic peaks related to that of the initial methyl oleate.

All functionalized products were identified by gas phase chromatographicanalysis coupled with a mass spectrometer as well as steric exclusionchromatograph.

Example 3

This example describes the synthesis of compounds functionalized at thestart by hexanal. Several unsaturated compounds were tested, such as1-octene, 4-octene and cyclooctene. These three tests led to theformation of 2-hydroxyoctyl hexanoate, 1-hydroxyoctan-2-yl hexanoate andoctane-1,2-diyl dihexanoate in the case of the reaction of 1-octene withhexanal; 5-hydroxyoctan-4-yl hexanoate and dihexanoate of cyclooctane;1,2 diyl for cyclooctene. These three reactions are illustrated inDiagrams 6, 7 and 8, below.

The reaction was conducted in a 100 ml glass reactor equipped withmechanical agitation. In all three cases, a weight of 15.0 g of theunsaturated compound was placed in the reactor. In the first case, the1-octene (Sigma-Aldrich-purity: 98%-batch 0001452135); in the second,4-octene (Sigma-Aldrich-purity: 90%-batch 10325JE); and in the thirdcase cyclooctene (Sigma-Aldrich-purity: 95%-batch 7238917). Then, 20.5 gof hexanal (Sigma-Aldrich-purity: 98%-batch S88145-279) were placed ineach reactor, along with 300 mg of solid catalyst of the ruthenium onsilica, containing 1.5% by weight of ruthenium. The medium was heated to80° C. under a constant bubbling air flow. The air flow rate wascontrolled by a ball flow meter and was 30 ml/min. After 7 hours ofreaction time, the air flow was stopped and the reaction medium wasplaced in an inert atmosphere (nitrogen). At the same time, the reactiontemperature was increased to 120° C. These parameters were maintainedfor 15 additional hours in all cases and for 70 hours in the case of the4-octene. Samples of the reaction medium were taken at regular intervalsin order to determine the progress of the reaction. The composition ofthe various reaction media after each reaction step is shown in Table 3,while the kinetic conversion curves for reagents and product yield inthe case of 4-octene are shown in the graph of FIG. 1:

TABLE 3 Conversion Functionalized Conversion to Epoxide productsDifunctionalized Type of Time to olefin hexanal yield yield productsyield olefin (hours) (%) (%) (%) (%) (%) 1-octene 7 78 100 10 3 6 22 90100 0 7 5 4-octene 7 84 100 51 2 0 22 96 100 27 26 2 77 100 100 0 10 10 cyclooctene 7 100 100 74 4 not avail. 22 100 100 69 3 not avail.

The quantitative composition of the various reaction media wasdetermined by gas phase chromatographic analysis. The AgilentTechnologies 6870N chromatograph used is as described in Example 1.

The temperature program of the furnace was as follows: 50° C. (5min.)-10° C./min.-100° C. (5 min.)-10° C./min.-150° C. (5 min.)-10°C./min.-220° C. (5 min.)-10° C./min.-250° C. (5 min.).

The hold times of the various products under the conditions describedpreviously, with a pressure level at the top of the column equal to16.32 psi, were as follows: 4-octene (2.9 min.); 1-octene (2.9 min.);cyclooctene (5.1 min.); hexanal (6.9 min.); dodecane (8.1 min.);4,5-epoxyoctane (8.1 min.); 1,2-epoxyoctane (9.6 min.); epoxycyclooctane(15.8 min.); 5-hydroxyoctan-4-yl hexanoate (26.6 min.); octane-4,5-diyldihexanoate (29.0 min.); octane-1,2-diyl dihexanoate (30.3 min.);2-hydroxyoctyl hexanoate and 1-hydroxyoctan-2-yl hexanoate (29.7 and31.6 min.); 2-hydroxycyclooctyl hexanoate (31.9 min.).

The conversion of reagents at time t is expressed as described inExample 1. The epoxidated product yield at time t was calculated asfollows: (number of moles of product at time t/(initial number of molesof the corresponding reagent*relative response coefficient of theproduct in relation to the reagent)*100.

The yield values of functionalized compounds were calculated in the samemanner but by assigning a response coefficient equal to one.

All the functionalized products were identified by gas phasechromatographic analysis coupled with mass spectrometry.

Example 4

This example relates to the synthesis of functionalized molecules from acompound of formula (II) and (III) which are the same, since themolecule used is 3-cyclohexene-1-carboxaldehyde with bothfunctionalities, unsaturation and aldehyde. The successive epoxidationand acylation reactions of this molecule lead first to the production ofthe intermediate epoxy-acid and then to the formation of dimers, trimersand oligomers of the initial compound, as shown in Diagram 9.

The reaction was carried out in a 100 ml glass reactor equipped withmechanical agitation. A weight of 30.0 g of3-cyclohexene-1-carboxaldehyde (Sigma-Aldrich-purity: 97%-batchMKBD1569) was placed in the reactor. The solid ruthenium on silicacatalyst, containing 1.5% by weight of ruthenium, was added to thereaction mixture at a rate of 1% by weight of the quantity of reagentengaged, i.e. 300 mg. The medium was heated to 80° C. in a continuousbubbling air flow. The air flow rate was controlled by a ball flow meterand was 70 ml/min. The reaction was conducted over 14 hours withoutreplacement of the air with nitrogen. The reaction temperature wasmaintained during the entire duration of the test at 80° C. Samples ofthe reaction medium were taken at regular intervals in order todetermine the status of the reaction. In this case, the status of thereaction was determined by steric exclusion chromatography. The resultsare presented in the form of a graph summarizing the kinetic curves ofthe status of the reaction in FIG. 2.

The composition of the reaction medium was determined by stericexclusion chromatography. The Alliance 2695 chromatograph from Waterswas equipped with a refraction index detector (RI 410) and two differentcolumns (Styragel®-HR 0.5 and Styragel®-HR 1). The temperature of thefurnace containing the columns was set at 30° C. and tetrahydrofurane(THF) was used as the eluent at a flow rate of 0.8 ml/min.

A calibration curve was plotted using polystyrene standards on a signalmeasurement base of the refraction index detector. These standardscomprised styrene polymers with a known molecular weight. Thiscalibration curve was plotted on a graph showing the base-10 logarithmof the molar weight in function of hold time. So, the variousby-products of the reaction were able to be identified by measuringtheir respective molecular weight.

Under the conditions for analysis described above, the hold times wereas follows: The term “monomers” used in the graph in FIG. 2 includes thereagent and the monomer products of the reaction;3-cyclohexene-1-carboxaldehyde (22.84 min.), 3-cyclohexene-1-carboxylicacid (21.54 min.), 3,4-epoxycyclohexane-1-carboxaldehyde (21.54 min.)and 3,4-epoxycyclohexane-1-carboxylic acid (20.90 min.). The term“dimers” includes all dimeric compounds (19.63+19.13+18.63 min.).Lastly, the term “trimers and oligomers” covers the compounds with thehighest molecular mass (18.32+17.75 min.).

Quantification was carried out based on the signal of the refractionindex detector, by assigning all components in the reaction medium aresponse coefficient equal to one. Therefore it was the proportion, interms of peak surface area, of each of them (or group of peaks) inrelation to the total surface area of all the peaks that was calculated.

Example 5

This example describes the synthesis of a thermoplastic polyurethaneobtained starting with a diol synthesized by the process that is thesubject of the invention. The diol in question was completely biosourcedand comes from the reaction of methyl oleate and hydroxycitronellal. Theapplication of the process to two reagents led to the synthesis ofmethyl 9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy)octadecanoate andof methyl 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy)octadecanoateas shown in Example No. 1. These two molecules are position isomers andrepresent the source of diol for the fabrication of polyurethane, thesource of diisocyanate being the 1,6-diisocyanatohexane (HMDI).

The functionalization reaction of the methyl oleate was conducted in aclosed reactor equipped with mechanical agitation, pressurized with pureoxygen and in the absence of any solvent. A weight of 10.0 g of methyloleate (Sigma Aldrich-purity: 99%-ref. 311111) as well as 29.0 g ofhydroxycitronellal (FCC grade-purity: ≧95-Sigma-Aldrich-ref. W258318)were placed in the reactor. The solid metal catalyst supported on silicacontains 1.5% by weight of metal and was added to the rectional mixtureat a ratio of 2% by weight of the methyl oleate quantity, i.e. 200 mg.The medium was heated to 70° C. and oxygen was introduced to a pressurelevel of 4 bars. This pressure level was kept constant by regularadditions of oxygen. The epoxidation reaction, the first step of the onepot process, was terminated after 2 hours (no further oxygenconsumption). At that moment, the epoxide yield was 90% with aselectivity of 95% (evaluated by gas chromatography using the methoddescribed in Example No. 1). Then the reactor was returned toatmospheric pressure, the reaction medium was degassed and any residualoxygen was vented by adding nitrogen. The temperature was increased to120° C. and the second step of the one pot process, the epoxide openingreaction, began. This step was much slower and took 48 hours.

Once the functionalization reaction was completed, the excesscitronellic acid present in the reaction medium was eliminated byliquid-liquid extraction. The reaction medium was diluted in diethylether then centrifuged in order to eliminate the solid catalyst. Theethereal organic phase was then placed in a vial in order to be decantedand an aqueous NaOH solution with a concentration of 0.3 M was added.Several successive washings of the organic phase were carried out with abasic solution, ending with a 0.05 M HCl solution. Lastly, a finalwashing was carried out with an NaCl saturated solution until theacidity was removed. The organic phase then was dried with sodiumcarbonate and the diethyl ether was evaporated via a rotary evaporator.At this point, the reaction medium consisted of 72% of the openingproduct (diol) according to the steric exclusion chromatography analysis(analysis method described in Example No. 1).

The polymerization reaction was also conducted in an inert (nitrogen)atmosphere. The diol obtained in the previous step was heated to 120° C.and the 1,6-diisocyanatohexane was added in a semi-molar quantity inrelation to the diol. After 2 hours of reaction time, the temperaturewas increased to 150° C. and a quantity of diisocyanate was added inorder to make the total quantity equimolar in relation to the diol. Thereaction continued for 2 additional hours.

In order to demonstrate the formation of a polyurethane, two analyticaltechniques were used: steric exclusion chromatography and infraredspectrometry. The former showed the evolution of the molar weight of theproduct, and the second demonstrated the formation of urethane bonds.

Steric exclusion chromatography analyses were conducted using a WatersAlliance 2695 chromatograph equipped with a refraction index detector(RI 410) and three different columns (Styrage® columns—HR 0.5-HR 1-HR3). The temperature of the furnace containing the columns was set at 30°C. and tetrahydrofurane (THF) was used as an eluent at a flow rate or0.8 ml/min.

A calibration curve, based on the molar weight logarithm for polystyrenestandards as a function of hold time was established. Four standardshaving a known molecular weight and molecular structure similar to thatof the functionalization product in question were analyzed in order todetermine the correction factor. The first part of Table 4 belowsummarizes the results of the analysis of the functionalized productbefore polymerization and the second part of the table, the resultsobtained upon completion of the polymerization step.

TABLE 4 Percentage Measured Corrected Hold time peak molecular molecular(min.) area weight weight Before 27.411 71.99 830 538 polymerization28.538 12.97 564 388 29.680 12.07 418 301 31.703 2.97 284 217 After 4hours 19.312 5.05 120,324 35,946 20.549 19.52 18,012 7,229 22.359 35.515,313 2,578 23.987 13.56 2,961 1,574 25.125 5.53 1,989 1,124 26.104 7.791,372 822 27.749 5.43 734 485 29.743 7.62 412 298

The initial mixture contained approximately 70% of the functionalizedproduct. After the polymerization reaction, the most representativeoligomers contain from 5 to 10 monomeric units with about 5% ofoligomers containing 50 units. Longer polymer chains are also probablypresent.

FIG. 3 shows the infrared spectra of the functionalized product in thepresence of diisocyanate before polymerization (t=0 min) and afterpolymerization (t=240 min).

One can observe the disappearance of the O—H bond absorption bandtowards 3400 cm⁻¹ to the benefit of the N—H bond band of the secondaryamino acid around 3,350 cm⁻¹. The disappearance of the peakcharacterizing isocyanates between 2,300 and 2,200 cm⁻¹ shows theirconversion. The increase in intensity of the C═O absorption band ofesters between 17,30 and 1,715 cm⁻¹ is due to the contribution of theC═O double bonds of the urethane functions. Lastly, the appearance ofpeaks at 1,520 cm⁻¹ and 1,250 cm⁻¹, characteristic of urethane bonds,may be observed.

Example 6

This example describes the synthesis of a thermo-hardening polyurethaneobtained from functionalized soy oil. The polyol obtained byfunctionalization of the soy oil in the presence of butyraldehyde wasused to produce polyurethane, and the diisocyanate was1,6-diisocyanatohexane (HMDI).

The functionalization reaction was conducted in a closed reactorequipped with mechanical agitation, pressurized with pure oxygen and inthe absence of any solvent. A weight of 10.0 g of refined soy oil(iodine index: 112.5 g I₂/100 g) as well as 30.0 g if butyraldehyde(Sigma-Aldrich-purity: 99%-ref. 538191) were placed into the reactor.The solid metal-type catalyst supported on silica contains 1.5% byweight of metal and was also added to the reaction mixture at a ratio of2% by weight of the quantity of methyl oleate used, i.e. 200 mg. Themedium was heated to 70° C. and oxygen was introduced until a pressurelevel of 4 bars was reached. This pressure level was kept constant bythe regular addition of oxygen. The epoxidation reaction, the first stepof the one pot process, was halted after 4 hours (no further oxygenconsumption). Then the reactor was brought back to atmospheric pressure,the reaction medium was degassed and the residual oxygen was displacedby the nitrogen. the temperature was increased to 120° C. and the secondstep of the one pot process began, i.e. the opening reaction of theepoxide that required 48 hours.

Once the functionalization reaction was completed, the excess butyricacid present in the reaction medium was eliminated by liquid-liquidextraction according to the protocol described in Example No. 5.

The polymerization reaction was conducted in an inert atmosphere(nitrogen). The polyol obtained in the preceding step was heated to 100°C. and 1,6 diisocyanatohexane was added in a very small quantity inorder to cause the polymerization reaction while keeping the mixture inthe liquid state necessary for chromatographic and spectrometricanalyses.

Steric exclusion chromatography analyses were conducted according to theprotocol of Example No. 5. The first part of Table 5 below summarizesthe results of the analysis of the functionalized product beforepolymerization and the second part of the table summarizes the resultsobtained after partial polymerization (since the thermohardened samplewas not soluble in THF).

TABLE 5 Measured Corrected Hold time Percentage molecular molecular(min.) peak area weight weight Before 22.729 23.02 4,580 2,274polymerization 23.501 19.62 3,486 1,806 25.075 57.37 2,026 1,142 After30 minutes 19.196 22.01 154,860 44,484 20.346 20.14 22,620 8,763 22.27318.23 5,513 2,660 23.301 12.57 3,731 1,913 25.115 27.04 1,996 1,128

The initial mixture contained approximately 77% of the functionalizedoil, which could contain up to 9 butyranoate functions. After thepartial polymerization reaction, the most representative oligomerscontained just 32 monomeric units. At this step, there remainedapproximately 40% of monomers but beyond this proportion, the mixturebecame solid and non-analyzable. For total polymerization, it isapparent that the molar weights are higher than those indicated.

FIG. 4 below shows the infrared spectra of the functionalized productbefore polymerization (t=0 min) and after polymerization (t=30 min.).

An attenuation of the absorption band of the of the O—H bond towards3,475 cm⁻¹ for the benefit of the band of the N—H bond of the secondaryamine towards 3,400 cm⁻¹ was observed. The appearance of peaks at 1,520cm⁻¹ and 1,250 cm⁻¹ that are characteristic of urethane bonds, were alsoobserved.

Example 7

This example illustrates the use of a catalyst for the second step ofthe one pot process between methyl oleate and hexanal, in order to formmethyl 9-(hexanoyloxy)-10-hydroxyoctadecanoate methyl10-(hexanoyloxy)-9-hydroxyoctadecanoate. The catalysts tested were:

-   -   solid acid catalysts. An Amberlyst® 15 (A15) polymer resin        functionalized by sulfonic functions (strong acid resin) and        four different Montmorillonites: One Montmorillonite (M) has a        specific surface area of 330 m²/g and a PZC (zero charge point)        of 2.8-3.8; a second (MAI) with a specific surface area of 250        m²/g and the PZC between 4 and 5; a third (MK10) with a specific        surface area of 250 m²/g and a PZC of 3.6; and the last one        (MKSF) having a specific surface area of between 20 and 40 m²/g.    -   solid basic catalysts. Two Amberlyst® polymer resins, one of        Type 21 (A21) functionalized by amino alkyls (low base resin)        and the other of Type 26 (A26) functionalized by quaternary        ammoniums (strong base resin). Calcium oxide (CaO) was also        tested, as was synthetic hydrotalcite (Mg₆Al₂(CO₃)(OH)₁₆.4H₂O).    -   homogenous catalysts. These are hexylamine, dihexylamine,        trihexylamine, and potassium hydroxide.

Each reaction was conducted in a 100 ml glass reactor equipped withmechanical agitation. In all cases, a weight of 20.0 g of hexanal(purity: 98%-Sigma Aldrich-ref. 115606) were placed into the reactor.The metal solid catalyst supported on silica contains 1.5% by weight ofruthenium and was added to the reaction mix at a ratio of 1% by weightof the volume of methyl ester engaged, i.e. 200 mg.

Then, the medium was heated to 80° C. with a flow of pure oxygen atatmospheric pressure. The air flow rate was controlled by a ball flowmeter and was 10 ml/min. After 7 hours of reaction, the methyl oleateconversion was at 89%, the hexanal conversion was at 96% and the epoxideyield was at 72%. At this moment, the air flow was stopped and thereaction medium was placed in an inert atmosphere (nitrogen). Thereaction medium was maintained at 80° C. and the opening catalyst wasadded at a ratio of 5% by weight for solid catalysts and 50 μl in thecase of hexylamines. In regards to potassium hydroxide, 50 μl of amethanolic solution with a concentration of 0.5 M were added. The mediumwas agitated for 24 additional hours.

FIG. 5 shows in graphical form the results obtained regarding theselectivity of functionalized products based on yield, upon completionof the one pot reaction, after 31 hours.

The composition of the reaction medium was determined by gas phasechromatographic analysis according to the protocol described in ExampleNo. 2.

The invention claimed is:
 1. A process for synthesizing multifunctionalcompounds comprising a reaction of a compound of formula (II) withatmospheric or molecular oxygen, in the presence of at least onealdehyde of formula (III), and optionally in the presence of at leastone catalyst or at least one radical initiator;

wherein: R¹⁰is H, or is selected from the group consisting of C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with each group optionally beingsubstituted by one or several groups, that are either identical ordifferent, selected from the group consisting of a halogen atom, —OH,—CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl,C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰; R²⁰ is H, cyano, a halogen atom, or—CHO, or is selected from the group consisting of C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂ arylC₁-C₆ alkyl with each groupoptionally being substituted by one or several groups, that are eitheridentical or different, selected from the group consisting of a halogenatom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰,C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CO₂R⁶⁰; R³⁰is selected from thegroup consisting of epoxy, —OCOR⁸, —CHO₂R⁸, C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂ aryl C₁-C₆ alkyl, with each groupoptionally being substituted by one or several groups, that are eitheridentical or different, selected from the group consisting of a halogenatom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰,C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CHO₂R⁶⁰; R⁴⁰is H, cyano, ahalogen atom, or —CHO, or is selected from the group consisting ofC₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with each groupoptionally being substituted by one or several groups, that are eitheridentical or different, selected from the group consisting of a halogenatom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, —OCOL²R⁵⁰, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOR⁸, and —CHO₂R⁶⁰; or R¹⁰and R³⁰may, with thecarbons to which they are bound, form a group selected from the groupconsisting of a C₅-C₁₂ cycloalkyl and a C₅-C₁₂ cycloalkenyl, with eachgroup optionally being substituted by one or several groups, that areeither identical or different, selected from the group consisting of ahalogen atom, —OH, —CHO, cyano, oxo, epoxy, —OCOR⁸, —CHO₂R⁶⁰, —OCOL²R⁵⁰,C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, and C₂-C₆ alkenyl; R⁵⁰is selected fromthe group consisting of H, —CHO, epoxy, a halogen atom, —OH, —SR⁸,cyano, nitro, isocyanate, C₁-C₂₀ alkyl, C₁-C₄ alkoxy, C₂ ⁻C₂₀ alkenyl,C₂ ⁻C₂₀ alkynyl, heterocycloalkyl, —CHO₂R⁸, and —NR⁹ ₂; L² is a singlecovalent bond, or is selected from the group consisting of C₁-C₂₀alkylene, C₃-C₁₂ cycloalkylene, C₂ ⁻C₁₂ alkenylene, C₅-C₁₂cycloalkenylene, C₆-C₁₂ arylene, heteroarylene, and heterocycloalkylene,with each group optionally being substituted by one or several groups,that are either identical or different, selected from the groupconsisting of a halogen atom, oxo, nitro, —CHO, —OH, —NR⁹ ₂, C₁-C₆alkyl, C₁-C₄ alkoxy, C₆-C₁₂ aryl C₁-C₆ alkyl, C₆-C₁₂ aryloxy, C₁-C₆alkyl C₆-C₁₂ aryl, C₁-C₆ hydroxyalkyl, and C₆-C₁₂ aryl; R⁶⁰is selectedfrom the group consisting of H and C₁-C₆ alkyl optionally substituted byone or several groups, that are either identical or different, selectedfrom the group consisting of —OH, —CHO, —O—CHOR⁷, and C₁-C₆ alkyl; R⁷ isselected from the group consisting of C₁-C₂₄ alkyl, C₂ ⁻C₂₀ alkenyl, and_(C) ₆-C₁₂ aryl, with each group being optionally substituted by one orseveral groups, that are either identical or different, selected fromthe group consisting of —OH, epoxy and —OCOL¹R⁵; R⁸ is H or C₁-C₆ alkyl;each identical or different R⁹ is selected from H, C₁-C₆ alkyl, orC₆-C₁₂ aryl L¹ is a single covalent bond, or is selected from the groupconsisting of C₁-C₂₀ alkylene, C₃-C₁₂ cycloalkylene, C_(2 -C) ₁₂alkenylene, C₅-C₁₂cycloalkenylene, C₆-C₁₂ arylene, heteroarylene, andheterocycloalkylene, with each group optionally being substituted by oneor several groups, that are either identical or different, selected fromthe group consisting of a halogen atom, —OH, oxo, nitro, —CHO, —OCOL¹R⁵,—CO₂R⁶⁰, —NR⁹ ₂,C₁-C₆ alkyl, C₁-C₄ alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy,C₆-C₁₂ aryl C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, and C₁-C₆alkyl C₆ ⁻C₁₂aryl; and R⁵ is selected from the group consisting of H, a halogen atom,—OH, —CHO, epoxy, —SR⁸, cyano, nitro, isocyanate, C₁-C₂₀ alkyl, C₁-C₄alkoxy, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, heterocycloalkyl, —CHO₂R⁸, and—NR⁹ ₂ ; wherein the reaction involves two successive steps comprising:an epoxidation of the compound of formula (II), generating an epoxidering, in the presence of molecular or atmospheric oxygen and of at leastone aldehyde of formula (III) and optionally in the presence of at leastone catalyst, and an opening of the epoxide ring, optionally in thepresence of at least one catalyst.
 2. The process according to claim 1,wherein the multifunctional compound is a compound having formula (Ia)or (Ib), a stereoisomer, a mixture thereof, an oligomer and/or a polymerthereof:

wherein: R¹ is H or is selected from the group consisting of C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, and C₆-C₁₂ aryl, with each group optionally beingsubstituted by one or several groups, that are either identical ordifferent, selected from the group consisting of a halogen atom, —OH,—CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl,—OCOL¹R⁵, —OCOR⁸, and —CO₂R⁶⁰ ; R² is H, cyano, or a halogen atom, or isselected from the group consisting of C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl,C₆-C₁₂ aryl, and C₆-C ₁₂ aryl C₁-C₆ alkyl, with each group optionallybeing substituted by one or several groups, that are either identical ordifferent, selected from the group consisting of a halogen atom, —OH,—CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl,—OCOL¹R⁵, —OCOR⁸, and —CO₂R^(60;) R³ is selected from the groupconsisting of epoxy, —OCOR⁸, —CO₂R⁸, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl,C₆-C₁₂ aryl, and _(C) _(6-C) ₁₂ aryl C₁-C₆ alkyl, with each groupoptionally being substituted by one or several groups, that are eitheridentical or different, selected from the group consisting of a halogenatom, —OH, —CHO, oxo, cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl,C₆-C₁₂ aryl, —OCOL¹R⁵, —OCOR⁸, and —CHO₂R⁶⁰; R⁴ is H, cyano, a halogenatom, or is selected from the group consisting of C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, and C₆ ⁻C₁₂ aryl, with each group optionally being substitutedby one or several groups, that are either identical or different,selected from the group consisting of a halogen atom, —OH, —CHO, oxo,cyano, —NR⁹ ₂, epoxy, C₁-C₄ alkoxy, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOL¹R⁵,—OCOR⁸, and —CHO₂R⁶⁰; or R¹ and R³ may, with the carbons to which theyare bound, form a group selected from the group consisting of a _(C)₅-C₁₂ cycloalkyl, and a _(C) ₅-C₁₂ cycloalkenyl, with each groupoptionally being substituted by one or several groups, that are eitheridentical or different, selected from the group consisting of a halogenatom,—OH, oxo, cyano, epoxy, —OCOL¹R⁵, —OCOR⁸, —CO₂R⁶⁰, C₁-C₆ alkyl,C₁-C₆ hydroxyalkyl, and C₂-C₆ alkenyl; R⁵ is selected from the groupconsisting of H, a halogen atom, —OH, —CHO, epoxy,—SR⁸, cyano, nitro,isocyanate, C₁-C₂₀ alkyl, C₁-C₄ alkoxy, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl,heterocycloalkyl, —CO₂R⁸, and —NR⁹ ₂; R⁶ is H or —CHO-L¹-R⁵; L¹ is asingle covalent bond, or is selected from the group consisting of C₁-C₂₀alkylene, C₃-C₁₂ cycloalkylene, C₂ ⁻C₁₂ alkenylene, C₅-C₁₂cycloalkenylene, C₆-C₁₂ arylene, heteroarylene, and heterocycloalkylene,with each group optionally being substituted by one or several groups,that are either identical or different, selected from the groupconsisting of a halogen atom, —OH, oxo, nitro, —CHO, —OCOL¹R⁵, —CHO₂R⁶⁰,—NR⁹ ₂, C₁-C₆ alkyl, C₁-C₄ alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, C₆-C₁₂aryl C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, and C₁-C₆alkyl C₆-C₁₂ aryl.
 3. Theprocess according to claim 1, wherein the reaction takes place in thepresence of a catalyst.
 4. The process according to claim 3, wherein thecatalyst is selected from the group consisting of catalysts with a basisof ruthenium, palladium, platinum, cobalt, manganese, nickel, copper,zinc, iron, and activated carbons.
 5. The process according to claim 3,wherein the catalyst is a supported ruthenium-based catalyst.
 6. Theprocess according to claim 1, wherein the compound of formula (II) is aC₃-C₂₀ alkene, or a C₅-C₁₂ cycloalkene, with each alkene or cycloalkenebeing optionally substituted by one or several identical or differentgroups selected from the group consisting of a halogen atom, —CHO, —OH,cyano, oxo, epoxy, —OCOR⁸, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₆-C₁₂ aryl,—OCOL²R⁵⁰, and —CHO₂R⁶⁰; with each alkyl, alkenyl or aryl beingoptionally substituted by one or several groups, that are identical ordifferent, selected from the group consisting of a halogen atom, oxo,—CHO, —OH, C₁-C₆ alkyl, C₆-C₁₂ aryl, —OCOL²R⁵⁰, —OCOR⁸, and —CO₂R⁶⁰. 7.The process according to claim 1, wherein the aldehyde of formula (III)is selected from the group consisting of formaldehyde, acetaldehyde,propanal, butyraldehyde, valeraldehyde, hexanal, heptanaldehyde,octanal, nonanaldehyde, decanal, undecanaldehyde, laurinaldehyde,tridecanaldehyde, isobutyraldehyde, isovaleraldehyde,2-methylbutyraldehyde, pivalaldehyde, 2-ethylbutaraldehyde,2ethylhexanaldehyde, isodecanaldehyde, acroleine, crotonaldehyde,trans-2-hexen-1-al, trans,trans-2,4-hexadien-1-al, cis-4-heptenal,trans-2-nonen-1-al, cis-4-decenal, citronellal, hydroxycitronellal,1-cyclohexene-1-carboxaldehyde, 3-cyclohexene-1-carboxaldehyde,benzaldehyde, 3- hydroxybenzaldehyde, 4-hydroxybenzaldehyde,4-methyl-2-phenyl-2-pentenal, aldehyde para-tertiarybutyl-alpha-methylhydrocinnamic, amylcinnamic aldehyde, glyoxal, glutaraldehyde,furfuraldehyde, 3-(methylthio)propionaldehyde, 2-ethylacroleine,3-methylcrotonaldehyde, 2-methyl-2-butenal, methyl 4-oxobutanoate,cinnamaldehyde, 3-dimethylaminoacroleine, cyclopentanecarboxaldehyde,2,3,4,5,6-pentafluorobenzaldehyde, 4-bromo-2,6-difluorobenzaldehyde,3,5-dibromobenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde,2,6-dinitrobenzaldehyde, 4-chlorobenzaldehyde, 2-chloro-4-hydroxybenzaldehyde, 4-fluorobenzaldehyde, 5-fluorosalicylaldehyde,4-nitrobenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde,3,5-dihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde,2-aminobenzaldehyde, 2,4-heptadienal, 2,2-dimethyl-4-pentenal,2-cyanobenzaldehyde, isophtalaldehyde, terephthalaldehyde,4-formylbenzoic acid, 5-formylsalicylic acid, o,m,p-tolualdehyde,phenylacetaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde,3-vinylbenzaldehyde, hydrocinnamaldehyde,4-hydroxy-3,5-dimethylbenzaldehyde, mesitaldehyde,2,4,6-trimethoxybenzaldehyde, 1-naphtaldehyde,biphenyl-4-carboxaldehyde, 3- phenoxybenzaldehyde,4-(4-formylphenoxy)benzaldehyde, diphenylacetaldehyde,9-anthracenecarboxaldehyde, 9-phenanthrenecarboxaldehyde,5-(hydroxymethyl)furfural, and tris(4-formylphenyl)amine.
 8. The processaccording to claim 1, wherein the epoxidation step is carried out at atemperature of between 0 and 200° C.
 9. The process according to claim8, wherein the epoxide opening step is carried out at a temperature ofbetween 0 and 300° C.
 10. The process according to claim 1,characterized in that it is carried out in the absence of any solvent.